si kr chemcomm 24:03:2019 - rsc.org · melting points were measured on a stuart® smp 10 melting...

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Supporting Information

A Kinetic Resolution Strategy for the Synthesis of Chiral Octahedral NHC-Iridium(III) Catalysts

Romane Manguin+a Delphine Pichon+a Robert Tarrieua Thomas Vivesa Thierry Roisnelb

Vincent Dorcetb Christophe Creacutevisya Karinne Miqueuc Ludovic Favereaub Jeanne

Crassousb Marc Mauduita and Olivier Basleacuteadagger

a Univ Rennes Ecole Nationale Supeacuterieure de Chimie de Rennes CNRS ISCR - UMR

6226 F-35000 Rennes France E-mail olivierbasleensc-rennesfr + These authors contributed equally to this work

dagger new adress LCC-CNRS Universiteacute de Toulouse CNRS Toulouse France

E-mail olivierbaslelcc-toulousefr

b Univ Rennes CNRS ISCR - UMR 6226 F-35000 Rennes France

E-mail ludovicfavereauuniv-rennes1fr

cCNRSUniv Pau amp Pays Adour Institut des Sciences Analytiques et de Physico-Chimie pour

lenvironnement et les Mateacuteriaux UMR 5254 Pau cedex 09 64000 France

E-mail karinnemiqueuuniv-paufr

Electronic Supplementary Material (ESI) for ChemCommThis journal is copy The Royal Society of Chemistry 2019

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Table of Contents 1 General Experimental procedures 3

2 Synthesis of Iridium-NHC complexes 4

21 Preparation of the imidazolium salts 4

22 Preparation of the silver-NHC complexes (S)-2 and (R)-2 5

23 Preparation of racemic [Ir(micro-Cl)(ppy)2]2 (1) 5

24 Preparation of the Iridium-NHC complexes 3 and 4 6

25 HPLC analyses for the Iridium-NHC complexes 3 and 4 8

26 Thermal and photochemical stability of D-(S)-4 9

3 Kinetic resolution studies 9

31 Preparation of racemic Ir-acac-5 9

32 HPLC analyses for reference samples 10

33 Kinetic resolution using the silver complex (S)-2 11

34 Kinetic resolution using the silver complex (R)-2 13

4 (Chiro)optical properties 15

41 UV-vis absorption 15

42 Emission spectra 15

43 Circularly Polarized Luminescence (CPL) 16

44 Electronic Circular Dichroism (ECD) 16

45 Vibrational Circular Dichroism (VCD) 18

46 Electrochemistry 21

5 Visible-light induced Ir-catalyzed Intermolecular [2+2] cycloaddition 22

6 Friedel Craft alkylation 23

61 General procedure for the synthesis of the Weinreb Amide 23

62 General procedure for the synthesis of acylimidazoles 24

63 Chiral Lewis-acid catalyzed Friedel Craft alkylation 25

7 NMR spectra 27

8 X-ray crystallographic data 40

9 Computational details 57

S3

1 General Experimental procedures

All commercial chemicals were used as received unless otherwise noted Toluene THF

dichloromethane and diethylether were dried and distilled using a Solvant Purification System (SPS)

MBRAUN Reactions were monitored by thin-layer chromatography (TLC) carried out on aluminium

backed silica gel 60 (F254) plates from MERCK (grain-size distribution 6020 mm) visualized using

254nm UV light and KMnO4K2CO3NaOH in water for staining Column chromatography was performed

with silica gel (spherical particle size 40 μm neutral) The eluents employed are reported as volume (volume percentages) Melting points were measured on a Stuartreg SMP 10 melting point apparatus in

open capillary tubes and are uncorrected Optical rotations were recorded on a polarimeter Optical

Activity Pekin Elmer 341 using a 1 mL cell with 1 dm path length All samples were carried out in acetone

or dichloromethane in 2 mL volumetric flask Specific rotations are reported in degdmminus1cm3gminus1 for a

wave length related to sodium line spectrum (589 nm) according to the Biot relation and are uncorrected

NMR spectra (proton carbon 2D) were recorded on a spectrometer of nuclear magnetic resonance

Bruker ARX-400 (1H 400 MHz 13C 100 MHz 19F 301 MHz 31P 162 MHz) with complete proton

decoupling for nucleus other than 1H Chemical shifts are reported in parts per million with the solvent resonance as the internal standard (CDCl3 1H δ 726 ppm 13C δ 7716 ppm CD2Cl2 1H δ 532 ppm 13C δ 5383 ppm CD3OD 1H δ 331 ppm 13C δ 4900 ppm CD3CN 1H δ 194 ppm 13C δ 132

11826 ppm) Coupling constants (J) are reported in hertz (Hz) Multiplicities in 1H NMR are reported

using following abbrevations s = singlet br s = broad singlet d = doublet dd = double doublet ddd =

double double doublet dt = double triplet t = triplet q = quartet quint = quintet sept = septet m =

multiplet Mass spectrometric analyses were performed at Centre Reacutegional de Mesures Physiques de

lrsquoOuest (CRMPO) Universiteacute de Rennes 1 High-resolution mass spectroscopy (HMRS) was recorded

on a Q-TOF spectrometer using electrospray ionization UV-Visible (UV-vis in M-1 cm-1) absorption spectra were recorded on a UV-2401PC Shimadzu spectrophotometer Fluorescence spectra were

recorded on a FL 920 Edimburgh fluorimeter Luminescence quantum yields Φ were measured in diluted

solution using the following equation where A(l) is the absorbance at the excitation wavelength λ n is

the refractive index D is the integrated intensity and ldquorrdquo and ldquoxrdquo stand for reference and sample

respectively

The fluorescence quantum yields were measured relative to [Ru(bpy)3]Cl2 in aqueous solution as the

standard (Φlum = 0042 ) estimated uncertainty in Φlum is plusmn 10 Excitation of reference and sample

compounds was performed at the same wavelength Electrochemical measurements were performed

with a potentiostat-galvanostat AutoLab PGSTAT 302N controlled by resident GPES (General Purpose

Electrochemical System 49) software using a conventional single-compartment three-electrode cell

The working and auxiliary electrodes were platinum electrodes and the reference electrode was the

saturated potassium chloride calomel electrode (SCE) Electronic circular dichroism (ECD in M-1 cm-1)

was measured on a Jasco J-815 Circular Dichroism Spectrometer (IFR140 facility - Biosit - Universiteacute

de Rennes 1) IR and VCD spectra were recorded on a Jasco FSV-6000 spectrometer The circularly

S4

polarized luminescence (CPL) measurements were performed using a home-built CPL

spectrofluoropolarimeter The samples were excited using a 90deg geometry with a Xenon ozone-free

lamp 150 W LS The following parameters were used emission slit width asymp 2 mm integration time = 4

sec scan speed = 50 nmmin accumulations = 5 The concentration of all the samples was ~10-5 M

Excitation of the samples were performed at 350 nm Enantiomeric excesses were measured on a

Alliance e2695 Watersreg HPLC with a UVvisible detector 2489 Watersreg at 254nm Single-crystal X-ray diffraction measurements were recorded on a D8 Venyure ASX diffractometer at T = 150K

2 Synthesis of Iridium-NHC complexes

21 Preparation of the imidazolium salts

The imidazolium salts were prepared according to the procedure reported by our laboratory1 In a round-

bottomed flask were placed 246-trimethylaniline (28 mL 20 mmol 10 equiv) (L or D)-Leucine (263

g 20 mmol 10 equiv) acetic acid (52 mL 90 mmol 45 equiv) and the mixture was heated at 60 degC for 5 min (mixture A) In another round bottomed flask were placed glyoxal (23 mL 20 mmol 10 equiv

40 wt in aqueous solution) formaldehyde (15 mL 20 mmol 10 equiv 37 wt in aqueous solution)

and acetic acid (52 mL 9 mmol 45 equiv) and the mixture was heated at 60 degC for 5 min (mixture B)

At 60 degC mixture B was added to mixture A (10 mL of AcOH was used to rince the flask) and the

resulting mixture was stirred at 60 degC for 1h then cooled down to room temperature Diethylether (200

mL) and water (200 mL) were added and the aqueous layer was washed with diethylether (3 x 200 mL)

Brine (100 mL) was added and the aqueous layer was washed with diethylether (3 x 200 mL) The aqueous layer was placed in a round-bottomed flask with dichloromethane (250 mL) and potassium

hexafluorophosphate (374 g 20 mmol 10 equiv) The biphasic mixture was stirred at room

temperature for one night The organic layer was separated dried over anhydrous magnesium sulphate

filtered and the solvent were evaporated under reduced pressure The desired imidazoliumPF6 salts

were isolated by column chromatography on silica gel (eluent system 100 DCM to 9010

DCMMeOH) The pure imidazoliumPF6 salts dissolved in a minimum of solvent (5050 acetone (HPLC

grade) Milli Q water) was loaded on ion exchange Dowexreg resin (activated by HCl 37 2 volumes)

and slowly eluted using the same eluent After removal of acetone and water under reduced pressure the residue was dissolved in CH2Cl2 dried over dried MgSO4 filtered and concentrated under reduced

pressure to afford the desired imidazolium chloride salts (S)-S1Cl or (R)-S1Cl

[1] C Jahier-Diallo M S T Morin P Queval M Rouen I Artur P Querard L Toupet C Creacutevisy O Basleacute M Mauduit Chem Eur J 2015 21 993-997

S5

(S)-S1Cl (beige solid 34 yield) (R)-S1Cl (beige solid 32 yield) 1H NMR

(400 MHz MeOD) δ (ppm) δ 940 (t J = 15Hz 1H) 799 (t J = 15 Hz 1H)

772 (t J = 15Hz 1H) 714 (s 2H) 515-510 (m 1H) 237 (s 3H) 217 (m

2H) 209 (s 3H) 209 (s 3H) 152-142 (m 1H) 103 (d J = 66 Hz 3H) 099

(d J = 66 Hz 3H) 13C NMR (100 MHz MeOD) δ (ppm) δ 1733 1426 1391

1359 1357 1326 1307 1288 1247 1246 648 424 266 231 215

211 173 173 LC-MS calcd for C18H24N2O2+ ([M]+) mz 30119 found mz

30100 (R)-S1Cl = -32 (plusmn 5 ) (CHCl3 312middot10-3 mol∙Lminus1)

22 Preparation of the silver-NHC complexes (S)-2 and (R)-2

The silver-NHC complexes were prepared according to the procedure reported by our laboratory2 In a

flame-dried 100 mL round-bottomed flask were placed the imidazolium chloride (S)-S1Cl or (R)-S1Cl (2 mmol 10 equiv) 3Å molecular sieves Ag2O (5 mmol 25 equiv) and dry DCM (23 mL) The resulting

mixture under argon atmosphere was vigorously stirred at room temperature overnight in dark Next

CH2Cl2 was removed under reduce pressure Then acetone was added and the mixture was filtered through a celite pad using acetone as eluent The filtered solution was concentrated and pentane was

added to induce precipitation The precipitate was washed twice with pentane The oligo- or polymeric

silver-NHC complexes (S)-2 and (R)-2 were obtained upon the removal of solvent residues under

vacuum and stored protected from light under an inert atmosphere

In agreement with the literature2 (S)-2 (beige solid 99 yield) (R)-2 (beige solid 90 yield) 1H NMR

(400 MHz CDCl3) δ (ppm) 741 (br s 1H) 691 (s 2H) 687 (s 1H) 524 (br s 1H) 232 (s 3H) 210

(br s 2H) 196 (s 2H) 188 (br s 2H) 132 (br s 1H) 099 (br s 3H) 089 (d J= 8 Hz 3H)

23 Preparation of racemic [Ir(micro-Cl)(ppy)2]2 (1)

Racemic [Ir(micro-Cl)(ppy)2]2 (1) was prepared according to a reported procedure (yellow powder 76 yield)3 In agreement with the literature 1H NMR (400 MHz CD2Cl2) δ (ppm)

927-924 (m 4H) 794 (d J = 82 Hz 4H) 782-777 (m 4H) 756 (dd J = 79

Hz 11 Hz 4H) 685-679 (m 8H) 663-658 (m 4H) 588 (dd J = 79 Hz 11

Hz 4H) 13C NMR (75 MHz CD2Cl2) δ (ppm) 1680 1514 1449 1440 1366

1304 1291 1237 1225 1213 1186

[2] J Thongpaen T E Schmid L Toupet V Dorcet M Mauduit and O Basleacute Chem Commun 2018 54 8202-8205 [3] Y Zhou H Gao X Wang and Honglan Qi Inorg Chem 2015 54 1446-1453

[ ]23Da

Cl

N

2

NIr

N N

O OH Cl

N N

O OH Cl

(S)-S1Cl

(R)-S1Cl

n

O OAg

N N

(R)-2

N N

AgO On (S)-2

S6

24 Preparation of the Iridium-NHC complexes 3 and 4

In a flamed-dried Schlenk tube under argon atmosphere the silver-NHC complex (S)-2 (152 mg 02 mmol 10 equiv) [Ir(micro-Cl)(ppy)2]2 1 (100 mg 01 mmol 05 equiv) were dissolved in distilled

dichloromethane (5 mL) The resulting mixture was warmed up to 40 degC and stirred in the dark for 16h

The resulting solution was filtered through a celite pad and concentrated under reduced pressure The

crude product with a diastereomeric ratio of about 21 determined by 1H NMR spectroscopy (fig S1)

was purified by column chromatography on silica gel (dichloromethaneacetone 955) to afford the

iridium complexes Λ-(S)-3 as a yellow solid (79 mg 49) and Δ-(S)-4 as a yellow solid (42 mg 26)

Figure S1 1H NMR spectra of the crude mixture

The same procedure has been followed for the synthesis of iridium complexes Δ-(R)-3 and Λ-(R)-4 that

are enantiomers of Λ-(S)-3 and Δ-(S)-4 respectively The crude product with a diastereomeric ratio of

about 21 determined by 1H NMR spectroscopy was purified by column chromatography on silica gel

(dichloromethaneacetone 955) to afford the iridium complexes Δ-(R)-3 as a yellow solid (75 mg 47)

and Λ-(R)-4 as a yellow solid (53 mg 33)

IrN

N

N N

OO

L-(S)-3

OO

N N

NN

Ir

D-(S)-4Ir-Cl-1

IrN

NCl

2

S7

Λ-(S)-3 and Δ-(R)-3 1H NMR (400 MHz CDCl3) δ

(ppm) 904 (d J = 59 Hz 1H) 872 (d J = 58 Hz 1H)

789 (d J = 83 Hz 1H) 775 (t J = 82 Hz 1H) 763 (t

J = 83 Hz 1H) 751 (d J = 77 Hz 1H) 748 (d J = 82

Hz 1H) 726 (d J = 21 Hz 1H) 712 (d J = 67 Hz

1H) 708 (d J = 66 Hz 1H) 687 (d J = 76 Hz 1H) 678 (t J = 77 Hz 1H) 668 (t J = 73 Hz 1H) 658 (d J = 19 Hz 1H) 650 (t J = 76 Hz 1H) 644

(t J = 74 Hz 1H) 637 (s 1H) 601 (s 1H) 594 (d J = 77 Hz 1H) 578 (d J = 76 Hz 1H) 472 (dd

J = 80 70 Hz 1H) 239 ndash 228 (m 1H) 213 (s 3H) 198 ndash 185 (m 1H) 173 (s 3H) 132 ndash 123

(m 1H) 096 (s 3H) 094 (d J = 62 Hz 3H) 082 (d J = 62 Hz 3H) 13C NMR (101 MHz CDCl3) δ

(ppm) 1745 1733 1715 1681 1647 1525 1494 1453 1441 1425 1381 1366 1358 1346

1344 1338 1311 1299 1296 1285 1282 1276 1239 1234 1226 1219 1216 1211 1199

1191 1184 1182 609 385 251 233 227 209 189 163 HRMS (ESI) calcd for

C40H39N4O2Na193Ir |M+Na]+ 82325946 mz found 8232601 (1 ppm) Anal Calcd for C40H39IrN4O2CH3OH C 5919 H 521 N 673 found C 5938 H 528 N 646 CalclOptical

rotation L-(S)-3 = +58 (plusmn 5 ) (CH2Cl2 21middot10-4 mol∙Lminus1) D-(R)-3 = -60 (plusmn 5 ) (CH2Cl2

21middot10-4 mol∙Lminus1)

Δ-(S)-4 and Λ-(R)-4 1H NMR (400 MHz CDCl3) δ

(ppm) 898 (d J = 51 Hz 1H) 845 (d J = 58 Hz 1H)

787 (d J = 84 Hz 1H) 774 (t J = 82 Hz 1H) 764 (t

J = 82 Hz 1H) 753 (d J = 80 Hz 1H) 749 (d J = 78 Hz 1H) 714 (t J = 74 Hz 1H) 706 ndash 695 (m 2H)

688 (d J = 77 Hz 1H) 677 (t J = 73 Hz 1H) 666 (t

J = 74 Hz 1H) 657 (d J = 19 Hz 1H) 645 (t J = 75 Hz 1H) 640 ndash 629 (m 2H) 601 (s 1H) 582

(d J = 78 Hz 1H) 579 (d J = 75 Hz 1H) 494 (dd J = 80 70 Hz 1H) 209 (s 3H) 188 (s 3H)

182 ndash 166 (m 1H) 163 ndash 151 (m 1H) 131 ndash 124 (m 1H) 094 (d J = 64 Hz 3H) 091 (d J = 64

Hz 3H) 077 (s 3Hl) 13C NMR (101 MHz CDCl3) δ (ppm) 1731 1715 1711 1681 1645 1543

1493 1456 1441 1427 1383 1366 1358 1351 1344 1341 1309 1299 1292 1290 1282

1277 1239 1236 1226 1220 1217 1213 1198 1185 1179 663 457 247 226 223 210 192 157 Anal Calcd for C40H39IrN4O2CH3OH C 5919 H 521 N 673 found C 5931 H

547 N 657 HRMS (ESI) calcd for C40H39N4O2Na193Ir [M+Na]+ 82325946 mz found 8232604

(1 ppm) Optical rotation D-(S)-4 = -32 (plusmn 5 ) (CH2Cl2 21middot10-4 mol∙Lminus1) L-(R)-4 = +30

(plusmn 5 ) (CH2Cl2 21middot10-4 mol∙Lminus1)

[ ]23Da [ ]23Da

[ ]23Da [ ]23Da

IrN

N

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(R)-3

IrN

N

N N

OO

Λ-(S)-3

S8

25 HPLC analyses for the Iridium-NHC complexes 3 and 4

The analyses were performed with a Daicel Chiralpack IA (250 x 46 mm) HPLC column on Waters system using a mobile phase composed of HexaneDCMEtOH (505006 vvv) The column temperature was 20 degC and UV-absorption was measured at 254 nm

Name Retention Time Area Area Height

1 L-(S)-3 14934 1651213 2080 28167

2 D-(R)-3 19353 1481456 1866 22306

3 L-(R)-4 28808 2311984 2913 14160

4 D-(S)-4 43480 2493060 3141 13653

Figure S2 HPLC trace for the mixture of L-(S)-3 D-(R)-3 L-(R)-4 and D-(S)-4

Name Retention Time Area Area Height 1 L-(S)-3 15954 2306622 10000 35774

Figure S3 HPLC trace for the isolated L-(S)-3

Name Retention Time Area Area Height 1 D-(R)-3 20203 7779711 10000 105913

Figure S4 HPLC trace for the isolated D-(R)-3

14934

19353

28808

43480

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Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

15954

AU

0000

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Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

20203

AU

000

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010

015

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

OO

N N

NN

Ir

Δ-(R)-3

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3Ir

NN

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(R)-3

S9

Name Retention Time Area Area Height 1 L-(R)-4 29383 4096582 10000 25270

Figure S5 HPLC trace for the isolated L-(R)-4


1 D-(S)-4 45556 4973589 10000 24208

Figure S6 HPLC trace for the isolated D-(S)-4

26 Thermal and photochemical stability of D-(S)-4

In a NMR tube a solution of D-(S)-4 (10 mg 0012 mmol) in CD2Cl2 (05 mL) was heated at 40 degC for 2

days and no epimerization could be detected by 1H NMR The same sample was then irradiated under

UV-light (365 nm) for one night and its HPLC analysis did not revealed any epimerization or structural

modification

3 Kinetic resolution studies

31 Preparation of racemic Ir-acac-5

Racemic [Ir(ppy)2(acac)] (5) was prepared according to a reported procedure (orange powder 80

yield)3 In agreement with the literature 1H NMR (CDCl3 400 MHz) δ 851 (ddd

2H J = 60 16 08 Hz) 784 (dd 2H J = 72 08 Hz) 772 (ddd 2H J = 84

76 16 Hz) 754 (dd 2H J = 80 12 Hz) 713 (ddd 2H J = 76 60 16 Hz)

680 (dt 2H J = 76 12 Hz) 668 (dt 2H J = 76 16 Hz) 626 (dt 2H J = 80 12 Hz) 521 (1H s) 178 (6H s) 13C NMR (75 MHz CD2Cl2) δ (ppm)

18471682 1482 1474 1451 1372 1332 1287 1238 1218 1208

1186 1003 283

[3] Y Zhou H Gao X Wang and Honglan Qi Inorg Chem 2015 54 1446-1453

29383

AU

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Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

45556

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

N

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

ONN

Ir

O

S10

32 HPLC analyses for reference samples

The analyses were performed with a Daicel Chiralpack IA (250 x 46 mm) HPLC column on Waters

system using a mobile phase composed of HexaneDCMEtOH (505006 vvv) The column

temperature was 20 degC and UV-absorption was measured at 254 nm


1 L-Cl-1 8459 100437 5013 5812

2 D-Cl-1 11259 99906 4987 4298

Figure S7 HPLC trace for racemic Ir-Cl-1


1 L-acac-5 8455 545111 5033 31569

2 D-acac-5 11257 538060 4967 23275

Figure S8 HPLC trace for racemic Ir-acac-5


1 L-acac-5 8499 600487 813 34613

2 D-acac-5 11320 578535 784 24897

3 L-(S)-3 15085 1303525 1766 21522

4 D-(R)-3 19524 1177706 1595 17415

5 L-(R)-4 29368 1791550 2427 11078

6 D-(S)-4 44065 1929780 2614 10703

Figure S9 HPLC trace for the reference mixture of 3 4 and 5

8459

11259

AU

0000

0002

0004

0006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8455

11257

AU

0000

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0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8499

11320

15085

19524

29368

44065AU

000

002

004

006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

rac-Ir-Cl-1

IrN

NCl

2

ONN

Ir

O

rac-Ir-acac-5

S11

33 Kinetic resolution using the silver complex (S)-2

Figure S10 Synthetic route to Λ-(S)-3 and enantioenriched Δ-Cl-1 and Δ-acac-5

In a NMR tube [Ir(micro-Cl)(ppy)2]2 1 (200 mg 00185 mmol 10 equiv) and (S)-2 (82 mg 001 mmol

054 equiv) were dissolved in CD2Cl2 (15 mL) The reaction was monitored by 1H NMR using 12-

dichloroethane as internal standard The HPLC analysis revealed the presence of L-(S)-3 (RT = 1501

min) as a single diastereoismer and the enantioenriched Ir-Cl-1 (RT = 1122 min (D-Cl-1) and RT = 843

min (L-Cl-1) (Fig S11) Then Ag(acac) (57 mg 0028 mmol 15 equiv) was added and the reaction

was monitored by 1H NMR After full conversion the reaction mixture was analyzed by HPLC and

demonstrated the full retention of configuration at metal center (Fig S12) The mixture of Ir(acac) and

Ir(NHC) complexes were separated on silica gel using DCMAcetone (100 to 91) as eluent to afford

the L-(S)-3 as yellow solid (132 mg 44 yield) and the D-acac-5 as orange solid (98 mg 43 yield)

DCE

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr

(05 equiv) CH2Cl2 rt

N N

AgO O2

Δ-(acac)-5 973 er

ONN

Ir

O

CH2Cl2 rtAg(acac)

Cl

N

2

Δ-(Cl)-1 973 er

NIr(S)-2

racemic ΛΔ (1 equiv)[Ir(micro-Cl)(ppy)2]2 (1)

N

Ir

N

Cl2

IrN

N

N N

OO

Λ-(S)-3

Cl

N

2

Δ-(Cl)-1

NIr

S12

DCE

Figure S11 1H NMR analyses for the kinetic resolution using the silver complex (S)-2 before (top) and

after (bottom) the addition of Ag(acac)





1 L-Cl-1 8438 13097 073 755

2 D-Cl-1 11216 567962 3171 24206

3 L-S-3 15012 1209965 6756 20418

4 D-S-3 - - - -

Figure S12 HPLC trace for the kinetic resolution using silver complex (S)-2 before Ag(acac)

8438

11216

15012

AU

0000

0010

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Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

Δ-(acac)-5

ONN

Ir

O

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr

Cl

N

2

Δ-(Cl)-1 973 er

NIr

S13


1 L-acac-5 8440 76761 142 4935

2 D-acac-5 11201 2544314 4708 109692

3 L-S-3 14563 2783501 5150 46214

4 D-S-3 - - - -

Figure S13 HPLC trace for the kinetic resolution using silver complex (S)-2 after Ag(acac)

34 Kinetic resolution using the silver complex (R)-2

Figure S14 Synthetic route to D-(R)-3 and enantioenriched L-Cl-1 and L-acac-5

In a NMR tube [Ir(micro-Cl)(ppy)2]2 1 (200 mg 00185 mmol 10 equiv) and (R)-2 (82 mg 001 mmol


dichloroethane as internal standard The HPLC analysis revealed the presence of D-(R)-3 (RT = 1955

min) as a single diastereoismer and the enantioenriched Ir-Cl-1 (RT = 844 min (L-Cl-1) and RT = 1124

min (D-Cl-1) (Fig S15) Then Ag(acac) (57 mg 0028 mmol 15 equiv) was added and the reaction


demonstrated the full retention of configuration at metal center (Fig S16) The mixture of Ir(acac) and Ir(NHC) complexes were separated on silica gel using DCMAcetone (100 to 91) as eluent to afford

the D-(R)-3 as yellow solid (143 mg 48 yield) and the L-acac-5 also as orange solid (10 mg 45

yield)

8440

11201

14563AU

000

005

010

015

020

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NOO

IrN

NCl

+

Δ-(R)-3 gt991 dr


N N

AgO O2

Λ-(acac)-5 973 er

CH2Cl2 rtAg(acac)

2

Λ-(Cl)-1 973 er

(R)-2O

O

N N

NN

Ir


N

Ir

N

Cl2

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr Δ-(acac)-5 973 er

ONN

Ir

O

S14





1 L-(Cl)-1 8438 547978 3816 31474

2 D-(Cl)-1 11241 19171 133 826

3 D-(R)-3 19550 868991 6051 12742

4 L-(R)-3 - - - -

Figure S15 HPLC trace for the kinetic resolution using silver complex (R)-2 before Ag(acac)


1 L-(acac)-5 8416 2085477 4106 118534

2 D-(acac)-5 11223 73549 145 3560

3 D-(R)-3 18901 2919531 5749 41707

4 L-(R)-4 - - - -

Figure S16 HPLC trace for the kinetic resolution using silver complex (R)-2 after Ag(acac)

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010

012

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NCl

+

Δ-(R)-3 gt991 dr

2

Λ-(Cl)-1 973 er

OO

N N

NN

Ir

IrN

NOO

Λ-(acac)-5 973 er Δ-(R)-3 gt991 dr

OO

N N

NN

Ir+

S15

4 (Chiro)optical properties

41 UV-vis absorption

CH2Cl2 solution at 298 K (~10-5 M) Figure S17 UV-vis absorption spectra of L-(S)-3 (blue) and D-(S)-4 (red) recorded in CH2Cl2 solution

at 298 K (~10-5 M)

42 Emission spectra

Figure S18 Luminescence spectra of L-(S)-3 (blue) and D-(S)-4 (red) at room temperature in CH2Cl2

solutions (solid lines) and in 2-MeTHF matrix at 77 K (dashed lines) and picture of the green

luminescence of L-(S)-3 at 77k excited at 365 nm (right)

Table S1 Non-polarized photophysical data including luminescence quantum yields (averaged values) and excited state lifetimes for the reported iridium complexes in degassed dichloromethane solution at 77K and 298 K

Compound Absorption lmax nm (e M-1

nm-1)

Emission lmax nm

fa t ns Emission 77 Kb E00

eV lmax nm t ns

D-(S)-4 267 (25700) 402 (2900) 478 (520)

508 520 (shoulder) 001a 851 487 522 558

(shoulder) 4400 255

L-(S)-3 267 (26100) 404 (3070) 480 (800)

508 518(shoulder) 001a 1048 487 522 558

(shoulder) 4500 255 aRelative to [Ru(bpy)3]Cl2 as the standard (Φlum = 0042) in degassed aqueous solution bIn 2-methyltetra- hydrofuran

S16

43 Circularly Polarized Luminescence (CPL)

Figure S19 Top Circularly polarized luminescence spectra of L-(S)-3 and D-(R)-3 (blue dotted and solid lines respectively) and of D-(S)-4 and L-(R)-4 (red solid and dotted lines respectively) bottom

total luminescence spectra of L-(S)-3 (blue) and D-(S)-4 (red) recorded in CH2Cl2 solution at 298 K (~10-5 M)

44 Electronic Circular Dichroism (ECD)

Figure S20 ECD spectra of L-(S)-3 and D-(R)-3 (blue dotted and solid lines respectively) and of D-(S)-4 and L-(R)-4 (red solid and dotted lines respectively) recorded in CH2Cl2 solution at 298 K (~10-5

M)

S17

Calculated ECD spectra were obtained from Time-Dependent Density Functional Theory (TD-DFT) calculations carried out with Gaussian 09 program To simulate the spectra 60 excited states were computed

Figure S21 a) Theoretical ECD spectra of (DIr RC)-3 and (DIr SC)-4 computed at SMD(DCM)-B3LYPSDD+f(Ir) 6-31G(HCNO) level of theory by taking into account solvent effect by SMD

model

D-(acac)-5 = -53 (plusmn 5 ) (CH2Cl2 10middot10-4 mol∙Lminus1)

L-(acac)-5 = +52 (plusmn 5 ) (CH2Cl2 10middot10-4 mol∙Lminus1)

Figure S22 UV-vis (top) and ECD (bottom) spectra of L-(acac)-5 and D-(acac)-5 (red and black solid lines respectively) recorded in CH2Cl2 solution at 298 K (~10-5 M)

-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1

(D Ir R C)-3 (D Ir S C)-4

[ ]23Da

[ ]23Da

S18

45 Vibrational Circular Dichroism (VCD)

IR and VCD spectra of enantiopure complexes 3 and 4 were recorded on a Jasco FSV-6000 spectrometer in CD2Cl2 in a 200 microns cell and at respective concentrations of 004 M and 009 M

Figure S23 a) Experimental VCD and b) IR spectra of (LIr SC)-3 (red) and (DIr RC)-3 (blue) in CD2Cl2

(C 004 M path-length 02 mm)

Figure S24 a) Experimental VCD and b) IR spectra of (DIr SC)-4 (red) and (LIr RC)-4 (blue) in CD2Cl2


-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19

Figure S25 a) Theoretical VCD spectrum of (LIr SC)-3 computed at SMD(CH2Cl2)- B3LYPSDD+f(Ir)6-31G(HCNO) level of theory by taking into account solvent effect by SMD

model Energies have been scaled by a factor of 098 b) Experimental VCD of (DIr SC)-3 (red) and (LIr RC)-3 (blue) in CD2Cl2 (C 004 M path-length 02 mm) c) Superimposition of theoretical (dotted

line) and experimental VCD spectra of (LIr SC)-3

-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20

Figure S26 a) Theoretical VCD spectrum of (DIr SC)-4 computed at SMD(CH2Cl2)-B3LYPSDD+f(Ir) 6-31G(HCNO) level of theory by taking into account solvent effect by SMD model Energies have

been scaled by a factor of 098 b) Experimental VCD of (DIr SC)-4 (red) and (LIr RC)-4 (blue) in CD2Cl2 (C 004 M path-length 02 mm) c) Superimposition of theoretical (dotted line) and

experimental VCD spectra of (DIr SC)-4

-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry

Figure S27 Cyclic voltammogram of L-(S)-3 versus saturated calomel electrode (SCE) as the

reference and 01 M Bu4NPF6 in CH2Cl2 as the electrolyte

Table S2 Oxidation potentials (EOx) of L-(S)-3 and D-(S)-4 referenced versus saturated calomel

electrode (SCE) and given in V

Compound EOx Ir(IV)Ir(III)

ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22

5 Visible-light induced Ir-catalyzed Intermolecular [2+2] cycloaddition

A quartz cuvette with a magnetic stir bar was charged with cinnamic acid 7 (02 mmol 10 equiv) 11-

diphenylethylene 8 (1 mmol 50 equiv) catalyst (1 mol) and dichloroethane (2 mL) The mixture was

bubbled with Ar for 10 minutes then sealed and irradiated at room temperature with 20W blue LED (lmax

= 460 nm) for 72 hours The solvent was removed under reduced pressure The desired product was

purified on silica gel (DCMMeOH 991 as eluent) as a white powder with 95 yield (64 mg 0195 mmol)

233-triphenylcyclobutane-1-carboxylic acid (9)4

1H NMR (400 MHz CD2Cl2) δ(ppm) 739 ndash 731 (m 4H) 727 ndash 712 (m 7H) 703 ndash

692 (m 4H) 459 (d J = 105 Hz 1H) 360 (m 1H) 342 (dd J = 116 83 Hz 1H)

273 (t J = 111 Hz 1H) 13C NMR (101 MHz CD2Cl2) δ (ppm) 1506 1413 1383

1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344

HPLC Analyses The analyses were performed with a Daicel Chiralpack IA (250 x 46 mm) HPLC column on Waters




1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789

Figure S28 HPLC trace for rac-9

[4] T Lei C Zhou M-Y Huang L-M Zhao B Yang C Ye H Xiao QY Meng V Ramamurthy C-H Tsung and L-Z Wu Angew Chem Int Ed 2017 56 15407ndash15410

Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh

Blue LEDS 48h rtClCH2CH2Cl 9

(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23

6 Friedel Craft alkylation

61 General procedure for the synthesis of the Weinreb Amide

In a flame-dried round-bottomed flask was added diethyl (2-(methoxy(methyl)amino)-2-

oxoethyl)phosphonate (12 equiv) in distilled THF (c = 04 M) At room temperature sodium hydride

(60 in oil 12 equiv) was added portionwise and the mixture was stirred under argon until the end of

the bubbling The mixture was cooled down to -78degC and the aldehyde (10 equiv) in THF solution (c = 04 M) was added dropwise The mixture was stirred for one hour at -78degC then warm up to room

temperature and stirred overnight under Argon The mixture was quenched with water and layers were

separated The organic layer was washed with NaHCO3 saturated solution and brine dried over MgSO4

filtered and concentrated under reduced pressure

(E)-3-([11-biphenyl]-4-yl)-N-methoxy-N-methylacrylamide was purified by silica gel chromatography

(dichloromethane) as a yellow powder with 95 yield (835 mg from

395 mmol) 1H NMR (400 MHz CDCl3) δ (ppm) 779 (d J = 160

Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)

708 (d J = 160 Hz 1H) 379 (s 3H) 333 (s 3H) 13C NMR (101 MHz CDCl3) δ (ppm) 1671 1431 1427 1404 1343 1290

1287 1279 1276 1272 1158 621 327 HRMS (ESI) mz = 2901151 calcd for C17H17NO2Na

[M+Na]+ 2901154 (1 ppm) mp 125-128degC

(E)-3-(3-isopropylphenyl)-N-methoxy-N-methylacrylamide5 was purified by silica gel chromatography

(pentanediethyl ether 6040) as a yellow powder with 70 yield (232 mg

from 324 mmol) 1H NMR (400 MHz CDCl3) δ (ppm) 773 (d J = 160 Hz

1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =

160 Hz) 377 (s 3H) 332 (s 3H) 299-288 (sept J = 69 Hz 1H) 127 (s

6H) 13C NMR (101 MHz CDCl3) δ (ppm) 1806 1495 1449 1349 1293 1288 1288 1272 1267 1224 364 341 240

[5] S Drissi-Amraoui T E Schmid J Lauberteaux C Creacutevisy O Basleacute R M de Figueiredo S Halbert H Geacuterard M Mauduit J-M campagne Adv Synth Catal 2016 358 2519-2540

H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe

NaH THF -78degC - rt 12h

R R

S24

62 General procedure for the synthesis of acylimidazoles

In a flame-dried schlenk was placed N-methylimidazole (15 equiv) in dry THF (c = 03 M) The solution

was cooled down to -78degC and n-BuLi (16M in hexane) was added dropwise The mixture was stirred

for 20 minutes and allowed to warm up to room temperature for 10 minutes The media was cooled

down at -78degC and a solution of the weinreb amide in dry THF (c = 03 M) was added dropwise The

mixture was quenched by NH4Cl saturated solution and stirred for an extra 10 minutes The organic

layer was separated and washed with NaHCO3 and brine dried over magnesium sulphate filtered and

concentrated under reduced pressure

(E)-3-([11-biphenyl]-4-yl)-N-methoxy-N-methylacrylamide (11a) was purified by silica gel

chromatography (pentanediethylether 6040) as a yellow powder with 86

yield (440 mg from 305 mmol)1H NMR (400 MHz CDCl3) δ (ppm) 810 (d J = 160 Hz 1H) 785 (d J = 160 Hz 1H) 778-774 (m 2H) 764-760

(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708

(s 1H) 410 (s 3H) 13C NMR (101 MHz CDCl3) δ (ppm) 1806 1442 1433 1431 1404 1341

1295 1294 1290 1280 1276 1274 1272 1228 365 HRMS (ESI) mz = 2891335 calcd for

C19H17NO2 [M+H]+ 2891337 (1 ppm) mp 133-136 degC

(E)-3-(3-isopropylphenyl)-1-(1-methyl-1H-imidazol-2-yl)prop-2-en-1-one (11b)5 was purified by

precipitation in pentane as a yellow powder with 82 yield (171 mg from

0729 mmol) 1H NMR (400 MHz CDCl3) δ (ppm) 806 (d J = 160 Hz 1H)

783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)

412 (s 3H) 297-290 (sept J = 69 Hz 1H) 128 (s 6H) 13C NMR (101

MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241

[5] S Drissi-Amraoui T E Schmid J Lauberteaux C Creacutevisy O Basleacute R M de Figueiredo S Halbert H Geacuterard M Mauduit

J-M campagne Adv Synth Catal 2016 358 2519-2540

N

OO

MeMe

O

N

N

N-methylimidazole n-BuLi THF

-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

63 Chiral Lewis-acid catalyzed Friedel Craft alkylation

In a round-bottomed flask to a solution of D-(Cl)-1 (0005 mmol 5 mol) in distilled THF (1 mL) under

Argon was added AgPF6 (001 mmol 10 mol) After being stirred at room temperature for 10 minutes

2-acyl imidazole (01 mmol 10 equiv) was added and the resulting mixture was also stirred for 10 minutes Then indole (025 mmol 25 equiv) was added at room temperature and the mixture was

stirred overnight and monitored by TLC The mixture was then concentrated under reduced pressure

and the desired product was purified by silica gel chromatography (pentaneAcOEt 7030)

3-([11-biphenyl]-4-yl)-3-(1H-indol-3-yl)-1-(1-methyl-1H-imidazol-2-yl)propan-1-one (12a)

Brown oil (25 mg 68 yield)1H NMR (400 MHz Chloroform-d) δ 811 (br 1H)

755 ndash 751 (m 3H) 746 (m 3H) 741 ndash 736 (m 2H) 733 ndash 727 (m 2H)

718 (dd J = 25 09 Hz 1H) 716 (d J = 09 Hz 1H) 714 ndash 711 (m 1H)

704 ndash 700 (m 1H) 699 (d J = 09 Hz 1H) 511 (td J = 77 09 Hz 1H) 404

(dd J = 165 77 Hz 1H) 391 (s 3H) 390 (dd J = 165 77 Hz 1H) 13C

NMR (101 MHz Methylene Chloride-d2) δ = 1909 1440 1433 1409 1389 1366 1289 1287 1284 1272 1271 1270 1269 1267 1221 1216

1192 1191 1111 451 379 360 247 HRMS (ESI) mz = 4281733 calcd for C27H23N3ONa

[M+Na] 4281734 (0 ppm) Optical rotation [a]$ = -350 (c = 1 CHCl3)


1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138

Figure S29 HPLC trace for rac-12a

Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549

Figure S30 HPLC trace for enantioenriched 12a

3-(1H-indol-3-yl)-3-(3-isopropylphenyl)-1-(1-methyl-1H-imidazol-2-yl)propan-1-one (12b)

Brown oil (20 mg 55 yield) 1H NMR (400 MHz CDCl3) d(ppm) 816 (br

1H) 751 (d J = 79 Hz 1H) 731-726 (m 2H) 719-709 (m 5H) 704-695 (m 3H) 505 (t J = 76 Hz 1H) 402 (dd J = 78 41 Hz 1H) 387 (s 3H)

383 (dd J = 78 41 Hz 1H) 282 (sept J = 69 Hz 1H) 119 (s 3H) 117 (s

3H) 13C NMR (101 MHz CDCl3) d (ppm) 1914 1488 1444 1366 1290

1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455

384 362 342 242 241 HRMS (ESI) mz = 3941890 calcd for C24H26N3ONa [M+Na]+ 3941886

(1 ppm) Optical rotation [a]$ = +320 (c = 1 CHCl3)


1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727

Figure S31 HPLC trace for rac-12b

26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568

Figure S32 HPLC trace for enantioenriched 12b

7 NMR spectra

1H NMR (400 MHz MeOD)

10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28

13C NMR (100 MHz MeOD)

1H NMR (400 MHz CDCl3)

n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29


13C NMR (100 MHz CDCl3)

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30

1H NMR (400 MHz CDCl3) δ (ppm)


OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40

8 X-ray crystallographic data

X-ray crystallographic study of L(S)-3 bull ORTEP of L(S)-3 CCDC ndeg 1894794

(C40H38IrN4O2 CHCl3 CH2Cl2) M = 100324 D8 VENTURE Bruker AXS diffractometer [] Mo-Kα

radiation (λ = 071073 Aring) T = 150 K orthorhombic P 21 21 21 (IT19) a = 93124(9) b = 167999(17)

c = 26446(2) Aring V = 41373(7) Aring3 Z = 4 d = 1611 gcm-3 μ = 3591 mm-1 The structure was solved

by dual-space algorithm using the SHELXT program [1] and then refined with full-matrix least-square

methods based on F2 (SHELXL-2014) [2] All non-hydrogen atoms were refined with anisotropic atomic

displacement parameters H atoms were finally included in their calculated positions A final refinement

on F2 with 9473 unique intensities and 445 parameters converged at ωR(F2) = 01170 (R(F) = 00438)

for 9331 observed reflections with I gt 2σ(I)

[1] G M Sheldrick Acta Cryst A71 (2015) 3-8

[2] Sheldrick GM Acta Cryst C71 (2015) 3-8

S41

Structural data Empirical formula C42 H41 Cl5 Ir N4 O2 Extended formula C40 H38 Ir N4 O2 C H Cl3 C H2 Cl2 Formula weight 100324 Temperature 150 K Wavelength 071073 Aring Crystal system space group orthorhombic P 21 21 21 Unit cell dimensions a = 93124(9) Aring α = 90 deg b = 167999(17) Aring β = 90 deg c = 26446(2) Aring γ = 90 deg Volume 41373(7) Aring3 Z Calculated density 4 1611 (gcm-3) Absorption coefficient 3591 mm-1 F(000) 1996 Crystal size 0510 x 0090 x 0060 mm Crystal color yellow Theta range for data collection 2319 to 27535 deg h_min h_max -12 12 k_min k_max -21 21 l_min l_max -34 32 Reflections collected unique 35458 9473 [R(int)a = 00323] Reflections [Igt2σ] 9331 Completeness to theta_max 0994 Absorption correction type multi-scan Max and min transmission 0806 0550 Refinement method Full-matrix least-squares on F2 Data restraints parameters 9473 0 445 Flack parameter 0026(13) bS (Goodness-of-fit) 1233 Final R indices [Igt2σ] R1c = 00438 wR2d = 01170 R indices (all data) R1c = 00445 wR2d = 01174 Largest diff peak and hole 3811 and -3060 e-Aring-3 aRint = sum |Fo2 - lt Fo2gt| sum[Fo2] bS = sum [w(Fo2 - Fc2)2] (n - p)12 cR1 = sum | |Fo| - |Fc| | sum |Fo| dwR2 = sum [w(Fo2 - Fc2)2] sum [w(Fo2)2]12 w = 1 [σ(Fo2) + aP2 + bP] where P = [2Fc2 + MAX(Fo2 0)] 3

Atomic coordinates site occupancy () and equivalent isotropic displacement parameters (Aring2) U(eq) is defined as one third of the trace of the orthogonalized Uij tensor

Atom x y z occ U(eq) Ir1 054037(4) 021624(2) 014998(2) 1 001026(10) N1 03432(9) 02345(5) 01842(3) 1 00122(18) C2 02739(13) 01826(7) 02137(4) 1 0018(2) H2 0316661 0133402 0219306 1 0021 C3 01437(13) 01971(8) 02364(5) 1 0023(3) H3 0097470 0157777 0255035 1 0028 C4 00826(12) 02727(8) 02305(5) 1 0024(3) H4 -0000414 0287110 0247775 1 0029 C5 01514(13) 03258(7) 01977(5) 1 0020(2) H5 0110418 0375339 0191723 1 0024 C6 02795(13) 03061(7) 01739(4) 1 00178(9) C7 03520(12) 03580(7) 01357(4) 1 00178(9) C8 03062(13) 04305(7) 01211(4) 1 00178(9) H8 0220410 0450465 0133861 1 0021 C9 03851(13) 04755(7) 00875(4) 1 00178(9) H9 0352205 0525143 0077063 1 0021 C10 05135(12) 04459(7) 00694(4) 1 00178(9) H10 0568139 0476281 0047162 1 0021 C11 05627(12) 03699(7) 00844(4) 1 00178(9)

S42

H11 0647132 0349880 0070537 1 0021 C12 04881(12) 03248(7) 01191(4) 1 00178(9) N21 07206(9) 02092(6) 01059(3) 1 00117(16) C22 08493(12) 02396(7) 01187(4) 1 0017(2) H22 0861207 0260668 0150954 1 0021 C23 09644(14) 02406(6) 00858(4) 1 0020(2) H23 1052464 0261715 0095544 1 0024 C24 09445(13) 02088(8) 00373(4) 1 0023(2) H24 1019536 0208989 0014130 1 0027 C25 08142(13) 01775(7) 00243(4) 1 0018(2) H25 0800762 0156450 -0007869 1 0022 C26 07013(12) 01770(7) 00589(4) 1 0015(2) C27 05580(12) 01481(6) 00495(4) 1 00134(19) C28 05138(13) 01099(7) 00053(4) 1 0020(2) H28 0579977 0100980 -0020463 1 0024 C29 03734(14) 00850(8) -00009(4) 1 0022(2) H29 0345966 0058999 -0030423 1 0026 C30 02738(13) 00987(7) 00368(5) 1 0020(2) H30 0179046 0082724 0032357 1 0024 C31 03147(12) 01367(7) 00818(4) 1 0017(2) H31 0246436 0146131 0106806 1 0020 C32 04553(13) 01603(6) 00895(4) 1 00128(18) O41 06612(8) 02843(5) 02071(3) 1 00149(14) C42 06797(11) 02652(6) 02537(4) 1 0014(2) O43 07645(9) 03023(5) 02820(3) 1 00211(18) C44 05914(12) 01961(6) 02736(4) 1 0016(2) H44 0490557 0207760 0265996 1 0019 C45 06015(14) 01809(7) 03304(4) 1 0019(2) H45 0644994 0135930 0344037 1 0023 C46 05338(16) 02462(7) 03629(4) 1 0022(2) H46 0596313 0293094 0361942 1 0027 C47 03819(15) 02713(11) 03462(7) 1 0047(4) H47A 0384738 0289655 0311872 1 0071 H47B 0348108 0313339 0367741 1 0071 H47C 0318221 0226529 0348713 1 0071 C48 0526(2) 02160(10) 04177(4) 1 0044(4) H48A 0452301 0176163 0420362 1 0066 H48B 0503639 0259581 0439830 1 0066 H48C 0616636 0193355 0427147 1 0066 N49 06315(11) 01245(5) 02440(3) 1 00134(17) C50 06978(13) 00567(7) 02636(4) 1 00169(13) H50 0729056 0048869 0296615 1 0020 C51 07072(13) 00050(7) 02248(4) 1 00169(13) H51 0743155 -0046630 0226376 1 0020 N52 06529(10) 00431(6) 01813(4) 1 00149(19) C53 06023(13) 01158(7) 01926(4) 1 00169(13) C54 06444(12) 00037(6) 01338(4) 1 0015(2) C55 05108(12) -00279(6) 01193(4) 1 0016(2) C56 05044(13) -00652(7) 00713(4) 1 0021(3) H56 0417623 -0086434 0060338 1 0025 C57 06238(16) -00710(7) 00404(5) 1 0024(3) C58 07544(14) -00425(7) 00579(5) 1 0024(3) H58 0836268 -0049423 0038238 1 0028 C59 07659(15) -00039(8) 01043(5) 1 0024(3) C60 03814(14) -00269(7) 01540(5) 1 0026(2) H60A 0410098 -0042365 0187404 1 0038 H60B 0310423 -0063440 0141548 1 0038 H60C 0341611 0025816 0154902 1 0038 C61 0607(2) -01069(10) -00113(5) 1 0038(4) H61A 0681304 -0145818 -0016584 1 0057 H61B 0614978 -0065925 -0036401 1 0057 H61C 0514984 -0132059 -0013836 1 0057 C62 09110(13) 00269(8) 01226(5) 1 0025(3) H62A 0905758 0038392 0158089 1 0038 H62B 0935196 0074586 0104443 1 0038 H62C 0983228 -0012749 0116684 1 0038 Cl11 09083(4) 04839(2) 024910(14) 1 00348(7) Cl12 08805(4) 04737(3) 014070(14) 1 00475(10) C101 07948(14) 04547(8) 01986(5) 1 0025(3) H101 0777875 0397258 0201279 1 0030 Cl13 06299(4) 05031(3) 020245(16) 1 00457(10) Cl21 04943(4) 08046(3) 087281(17) 1 00542(12) Cl22 05978(6) 06721(3) 09354(2) 1 00629(13) C202 0527(2) 06981(9) 08756(5) 1 0043(4) H20A 0438023 0669570 0869802 1 0052 H20B 0594469 0683044 0849266 1 0052

S43

Anisotropic displacement parameters (Aring2)

The anisotropic displacement factor exponent takes the form -2π2 [ h2 a2 U11 + + 2 h k a b U12 ]

Atom U11 U22 U33 U23 U13 U12 Ir1 001125(15) 001207(15) 000747(15) -000023(15) 000103(15) 000264(15) N1 0008(4) 0015(5) 0014(4) -0006(3) 0003(3) 0003(3) C2 0019(5) 0018(5) 0016(5) -0003(4) 0003(4) 0001(4) C3 0018(5) 0030(7) 0020(6) -0004(5) 0006(4) -0003(5) C4 0012(5) 0025(7) 0035(7) 0001(5) -0005(4) 0002(4) C5 0016(5) 0024(6) 0021(6) -0003(5) 0000(4) 0007(4) C6 0019(2) 0019(2) 0016(2) 00029(16) -00026(16) 00048(17) C7 0019(2) 0019(2) 0016(2) 00029(16) -00026(16) 00048(17) C8 0019(2) 0019(2) 0016(2) 00029(16) -00026(16) 00048(17) C9 0019(2) 0019(2) 0016(2) 00029(16) -00026(16) 00048(17) C10 0019(2) 0019(2) 0016(2) 00029(16) -00026(16) 00048(17) C11 0019(2) 0019(2) 0016(2) 00029(16) -00026(16) 00048(17) C12 0019(2) 0019(2) 0016(2) 00029(16) -00026(16) 00048(17) N21 0015(4) 0016(4) 0004(3) -0001(3) 0004(3) 0000(4) C22 0019(5) 0017(5) 0016(5) 0002(4) 0003(4) 0003(4) C23 0014(5) 0021(5) 0025(5) -0001(4) 0001(5) -0004(5) C24 0019(5) 0029(6) 0019(5) 0000(5) 0013(4) 0001(6) C25 0025(6) 0020(6) 0009(5) -0004(4) 0004(4) 0006(5) C26 0014(5) 0020(5) 0010(5) -0001(4) 0003(4) 0002(4) C27 0014(5) 0012(4) 0014(4) 0000(4) -0003(4) 0000(4) C28 0020(6) 0027(6) 0012(5) -0002(4) -0001(4) 0004(4) C29 0025(6) 0026(6) 0014(5) -0006(5) -0004(5) 0005(5) C30 0017(5) 0023(6) 0021(6) -0005(5) -0003(4) 0003(4) C31 0016(5) 0019(5) 0015(5) -0002(4) -0002(4) 0001(4) C32 0015(5) 0010(4) 0013(4) 0001(3) 0001(4) 0003(4) O41 0021(4) 0015(3) 0009(3) -0002(3) 0000(3) -0004(4) C42 0015(5) 0018(6) 0010(5) -0001(4) 0003(4) 0002(4) O43 0019(4) 0028(5) 0016(4) -0003(3) 0001(3) -0007(3) C44 0018(5) 0019(6) 0011(5) -0003(4) 0001(4) 0002(4) C45 0029(6) 0023(6) 0006(4) 0002(4) 0003(4) 0000(5) C46 0027(6) 0030(6) 0010(5) -0001(4) 0001(5) -0004(6) C47 0026(6) 0065(11) 0051(9) -0032(10) 0007(7) 0008(7) C48 0079(11) 0035(7) 0017(5) -0012(6) 0015(7) 0000(10) N49 0023(5) 0010(4) 0008(4) 0000(3) 0001(4) 0004(4) C50 0024(3) 0013(3) 0014(3) 0004(2) 0001(2) 0004(2) C51 0024(3) 0013(3) 0014(3) 0004(2) 0001(2) 0004(2) N52 0015(4) 0013(4) 0017(5) -0007(4) 0004(4) 0002(3) C53 0024(3) 0013(3) 0014(3) 0004(2) 0001(2) 0004(2) C54 0020(5) 0010(5) 0014(5) 0004(4) 0000(4) 0003(4) C55 0018(5) 0015(5) 0014(5) -0001(4) 0001(4) -0002(4) C56 0028(7) 0015(5) 0020(5) -0001(4) 0000(4) -0003(4) C57 0038(7) 0017(6) 0018(6) -0003(4) 0005(5) 0002(5) C58 0026(6) 0022(6) 0023(6) 0002(5) 0012(5) 0009(5) C59 0024(6) 0021(6) 0028(7) -0002(5) 0013(5) 0005(5) C60 0031(6) 0028(6) 0018(6) 0001(5) 0008(6) 0004(5) C61 0057(10) 0038(8) 0020(7) -0009(6) 0010(6) -0006(7) C62 0020(6) 0027(6) 0029(7) 0001(5) -0001(5) 0005(5) Cl11 00320(16) 00378(18) 00345(18) -00072(15) -00100(14) 00050(14) Cl12 00369(19) 0079(3) 00266(19) 00063(18) 00048(15) -00026(19) C101 0021(6) 0028(6) 0027(6) -0005(5) 0005(5) -0005(5) Cl13 00276(18) 0067(3) 0043(2) -00201(19) -00081(15) 00224(18) Cl21 0043(2) 0074(3) 0046(2) -0016(2) -00065(16) 00052(19) Cl22 0066(3) 0071(3) 0052(3) 0000(2) -0002(2) -0006(3) C202 0050(9) 0047(9) 0033(7) -0011(6) 0007(7) 0004(8)

Bond lengths [Aring]

Ir1 - C32 = 2017(10) Ir1 - N21 = 2047(8) Ir1 - C12 = 2057(11) Ir1 - N1 = 2070(8) Ir1 - C53 = 2110(11)

S44

Ir1 - O41 = 2204(7) N1 - C2 = 1336(15) N1 - C6 = 1369(14) C2 - C3 = 1374(16) C2 - H2 = 09300 C3 - C4 = 1401(18) C3 - H3 = 09300 C4 - C5 = 1399(18) C4 - H4 = 09300 C5 - C6 = 1389(16) C5 - H5 = 09300 C6 - C7 = 1496(16) C7 - C8 = 1347(16) C7 - C12 = 1453(16) C8 - C9 = 1380(16) C8 - H8 = 09300 C9 - C10 = 1380(16) C9 - H9 = 09300 C10 - C11 = 1414(15) C10 - H10 = 09300 C11 - C12 = 1377(16) C11 - H11 = 09300 N21 - C22 = 1346(14) N21 - C26 = 1367(13) C22 - C23 = 1380(16) C22 - H22 = 09300 C23 - C24 = 1402(16) C23 - H23 = 09300 C24 - C25 = 1366(17) C24 - H24 = 09300 C25 - C26 = 1394(15) C25 - H25 = 09300 C26 - C27 = 1442(15) C27 - C28 = 1397(15) C27 - C32 = 1440(15) C28 - C29 = 1383(17) C28 - H28 = 09300 C29 - C30 = 1382(17) C29 - H29 = 09300 C30 - C31 = 1403(16) C30 - H30 = 09300 C31 - C32 = 1383(16) C31 - H31 = 09300 O41 - C42 = 1282(13) C42 - O43 = 1254(13) C42 - C44 = 1518(15) C44 - N49 = 1483(13) C44 - C45 = 1526(15) C44 - H44 = 09800 C45 - C46 = 1529(16) C45 - H45 = 09300 C46 - C48 = 1538(16) C46 - C47 = 1540(19) C46 - H46 = 09800 C47 - H47A = 09600 C47 - H47B = 09600 C47 - H47C = 09600 C48 - H48A = 09600 C48 - H48B = 09600 C48 - H48C = 09600 N49 - C50 = 1395(14) N49 - C53 = 1393(14) C50 - C51 = 1348(16) C50 - H50 = 09300 C51 - N52 = 1411(14) C51 - H51 = 09300 N52 - C53 = 1343(14) N52 - C54 = 1422(14) C54 - C59 = 1380(17) C54 - C55 = 1406(15) C55 - C56 = 1415(15) C55 - C60 = 1515(16) C56 - C57 = 1385(17) C56 - H56 = 09300 C57 - C58 = 1387(19) C57 - C61 = 1501(17) C58 - C59 = 1392(19)

S45

C58 - H58 = 09300 C59 - C62 = 1526(19) C60 - H60A = 09600 C60 - H60B = 09600 C60 - H60C = 09600 C61 - H61A = 09600 C61 - H61B = 09600 C61 - H61C = 09600 C62 - H62A = 09600 C62 - H62B = 09600 C62 - H62C = 09600 Cl11 - C101 = 1772(14) Cl12 - C101 = 1757(13) C101 - Cl13 = 1740(14) C101 - H101 = 09800 Cl21 - C202 = 1817(17) Cl22 - C202 = 1769(17) C202 - H20A = 09700 C202 - H20B = 09700

Angles [deg]

C32 - Ir1 - N21 = 8100(4) C32 - Ir1 - C12 = 9030(4) N21 - Ir1 - C12 = 9110(4) C32 - Ir1 - N1 = 9390(4) N21 - Ir1 - N1 = 17000(4) C12 - Ir1 - N1 = 8040(4) C32 - Ir1 - C53 = 9920(4) N21 - Ir1 - C53 = 9200(4) C12 - Ir1 - C53 = 17040(5) N1 - Ir1 - C53 = 9730(4) C32 - Ir1 - O41 = 17040(4) N21 - Ir1 - O41 = 9010(3) C12 - Ir1 - O41 = 8620(4) N1 - Ir1 - O41 = 9440(3) C53 - Ir1 - O41 = 8470(4) C2 - N1 - C6 = 11860(9) C2 - N1 - Ir1 = 12600(7) C6 - N1 - Ir1 = 11530(7) N1 - C2 - C3 = 12450(11) N1 - C2 - H2 = 11770 C3 - C2 - H2 = 11770 C2 - C3 - C4 = 11800(11) C2 - C3 - H3 = 12100 C4 - C3 - H3 = 12100 C5 - C4 - C3 = 11740(11) C5 - C4 - H4 = 12130 C3 - C4 - H4 = 12130 C6 - C5 - C4 = 12150(11) C6 - C5 - H5 = 11920 C4 - C5 - H5 = 11920 N1 - C6 - C5 = 11940(11) N1 - C6 - C7 = 11680(10) C5 - C6 - C7 = 12370(10) C8 - C7 - C12 = 12240(11) C8 - C7 - C6 = 12530(11) C12 - C7 - C6 = 11200(10) C7 - C8 - C9 = 12080(11) C7 - C8 - H8 = 11960 C9 - C8 - H8 = 11960 C8 - C9 - C10 = 11920(11) C8 - C9 - H9 = 12040 C10 - C9 - H9 = 12040 C9 - C10 - C11 = 12060(11) C9 - C10 - H10 = 11970 C11 - C10 - H10 = 11970 C12 - C11 - C10 = 12130(11) C12 - C11 - H11 = 11930 C10 - C11 - H11 = 11930 C11 - C12 - C7 = 11550(10) C11 - C12 - Ir1 = 12920(8) C7 - C12 - Ir1 = 11520(8)

S46

C22 - N21 - C26 = 11970(9) C22 - N21 - Ir1 = 12440(7) C26 - N21 - Ir1 = 11560(7) N21 - C22 - C23 = 12250(10) N21 - C22 - H22 = 11870 C23 - C22 - H22 = 11870 C22 - C23 - C24 = 11800(11) C22 - C23 - H23 = 12100 C24 - C23 - H23 = 12100 C25 - C24 - C23 = 11970(10) C25 - C24 - H24 = 12020 C23 - C24 - H24 = 12020 C24 - C25 - C26 = 12040(10) C24 - C25 - H25 = 11980 C26 - C25 - H25 = 11980 N21 - C26 - C25 = 11970(10) N21 - C26 - C27 = 11430(9) C25 - C26 - C27 = 12590(10) C28 - C27 - C32 = 11900(10) C28 - C27 - C26 = 12490(10) C32 - C27 - C26 = 11610(9) C29 - C28 - C27 = 12110(11) C29 - C28 - H28 = 11950 C27 - C28 - H28 = 11950 C30 - C29 - C28 = 11990(11) C30 - C29 - H29 = 12000 C28 - C29 - H29 = 12000 C29 - C30 - C31 = 12040(11) C29 - C30 - H30 = 11980 C31 - C30 - H30 = 11980 C32 - C31 - C30 = 12080(11) C32 - C31 - H31 = 11960 C30 - C31 - H31 = 11960 C31 - C32 - C27 = 11870(10) C31 - C32 - Ir1 = 12840(8) C27 - C32 - Ir1 = 11280(8) C42 - O41 - Ir1 = 12670(7) O43 - C42 - O41 = 12230(10) O43 - C42 - C44 = 12090(10) O41 - C42 - C44 = 11680(9) N49 - C44 - C42 = 10750(9) N49 - C44 - C45 = 11160(9) C42 - C44 - C45 = 11590(9) N49 - C44 - H44 = 10710 C42 - C44 - H44 = 10710 C45 - C44 - H44 = 10710 C44 - C45 - C46 = 11400(10) C44 - C45 - H45 = 12300 C46 - C45 - H45 = 12300 C45 - C46 - C48 = 10820(11) C45 - C46 - C47 = 11450(11) C48 - C46 - C47 = 10840(13) C45 - C46 - H46 = 10850 C48 - C46 - H46 = 10850 C47 - C46 - H46 = 10850 C46 - C47 - H47A = 10950 C46 - C47 - H47B = 10950 H47A - C47 - H47B = 10950 C46 - C47 - H47C = 10950 H47A - C47 - H47C = 10950 H47B - C47 - H47C = 10950 C46 - C48 - H48A = 10950 C46 - C48 - H48B = 10950 H48A - C48 - H48B = 10950 C46 - C48 - H48C = 10950 H48A - C48 - H48C = 10950 H48B - C48 - H48C = 10950 C50 - N49 - C53 = 11130(9) C50 - N49 - C44 = 12530(9) C53 - N49 - C44 = 12340(9) C51 - C50 - N49 = 10580(10) C51 - C50 - H50 = 12710 N49 - C50 - H50 = 12710 C50 - C51 - N52 = 10770(10) C50 - C51 - H51 = 12610 N52 - C51 - H51 = 12610 C53 - N52 - C51 = 11090(9)

S47

C53 - N52 - C54 = 12700(10) C51 - N52 - C54 = 12190(9) N52 - C53 - N49 = 10420(9) N52 - C53 - Ir1 = 13470(8) N49 - C53 - Ir1 = 11940(8) C59 - C54 - C55 = 12240(11) C59 - C54 - N52 = 11980(11) C55 - C54 - N52 = 11780(10) C54 - C55 - C56 = 11670(10) C54 - C55 - C60 = 12230(10) C56 - C55 - C60 = 12090(10) C57 - C56 - C55 = 12180(11) C57 - C56 - H56 = 11910 C55 - C56 - H56 = 11910 C56 - C57 - C58 = 11880(11) C56 - C57 - C61 = 11890(13) C58 - C57 - C61 = 12220(13) C57 - C58 - C59 = 12150(11) C57 - C58 - H58 = 11920 C59 - C58 - H58 = 11920 C54 - C59 - C58 = 11860(13) C54 - C59 - C62 = 12100(12) C58 - C59 - C62 = 12040(11) C55 - C60 - H60A = 10950 C55 - C60 - H60B = 10950 H60A - C60 - H60B = 10950 C55 - C60 - H60C = 10950 H60A - C60 - H60C = 10950 H60B - C60 - H60C = 10950 C57 - C61 - H61A = 10950 C57 - C61 - H61B = 10950 H61A - C61 - H61B = 10950 C57 - C61 - H61C = 10950 H61A - C61 - H61C = 10950 H61B - C61 - H61C = 10950 C59 - C62 - H62A = 10950 C59 - C62 - H62B = 10950 H62A - C62 - H62B = 10950 C59 - C62 - H62C = 10950 H62A - C62 - H62C = 10950 H62B - C62 - H62C = 10950 Cl13 - C101 - Cl12 = 11150(8) Cl13 - C101 - Cl11 = 11060(7) Cl12 - C101 - Cl11 = 10960(7) Cl13 - C101 - H101 = 10830 Cl12 - C101 - H101 = 10830 Cl11 - C101 - H101 = 10830 Cl22 - C202 - Cl21 = 10990(8) Cl22 - C202 - H20A = 10970 Cl21 - C202 - H20A = 10970 Cl22 - C202 - H20B = 10970 Cl21 - C202 - H20B = 10970 H20A - C202 - H20B = 10820

Torsion angles [deg]

C6 - N1 - C2 - C3 = -250(17) Ir1 - N1 - C2 - C3 = 17920(9) N1 - C2 - C3 - C4 = -370(18) C2 - C3 - C4 - C5 = 640(17) C3 - C4 - C5 - C6 = -340(18) C2 - N1 - C6 - C5 = 550(16) Ir1 - N1 - C6 - C5 = -17590(9) C2 - N1 - C6 - C7 = -17260(10) Ir1 - N1 - C6 - C7 = 590(13) C4 - C5 - C6 - N1 = -260(18) C4 - C5 - C6 - C7 = 17540(11) N1 - C6 - C7 - C8 = -17940(11) C5 - C6 - C7 - C8 = 260(19) N1 - C6 - C7 - C12 = -510(14) C5 - C6 - C7 - C12 = 17690(11) C12 - C7 - C8 - C9 = 290(18) C6 - C7 - C8 - C9 = 17660(11)

S48

C7 - C8 - C9 - C10 = -110(18) C8 - C9 - C10 - C11 = 110(17) C9 - C10 - C11 - C12 = -310(17) C10 - C11 - C12 - C7 = 460(16) C10 - C11 - C12 - Ir1 = -17640(9) C8 - C7 - C12 - C11 = -450(17) C6 - C7 - C12 - C11 = -17900(10) C8 - C7 - C12 - Ir1 = 17630(9) C6 - C7 - C12 - Ir1 = 180(12) C26 - N21 - C22 - C23 = 080(17) Ir1 - N21 - C22 - C23 = -17340(8) N21 - C22 - C23 - C24 = 020(17) C22 - C23 - C24 - C25 = -060(18) C23 - C24 - C25 - C26 = -010(18) C22 - N21 - C26 - C25 = -150(16) Ir1 - N21 - C26 - C25 = 17320(8) C22 - N21 - C26 - C27 = -17880(10) Ir1 - N21 - C26 - C27 = -410(12) C24 - C25 - C26 - N21 = 110(18) C24 - C25 - C26 - C27 = 17810(11) N21 - C26 - C27 - C28 = -17720(10) C25 - C26 - C27 - C28 = 570(18) N21 - C26 - C27 - C32 = 270(14) C25 - C26 - C27 - C32 = -17440(11) C32 - C27 - C28 - C29 = 110(17) C26 - C27 - C28 - C29 = -17910(11) C27 - C28 - C29 - C30 = 080(19) C28 - C29 - C30 - C31 = -100(19) C29 - C30 - C31 - C32 = -060(18) C30 - C31 - C32 - C27 = 250(16) C30 - C31 - C32 - Ir1 = 17950(8) C28 - C27 - C32 - C31 = -270(15) C26 - C27 - C32 - C31 = 17740(10) C28 - C27 - C32 - Ir1 = 17990(8) C26 - C27 - C32 - Ir1 = 000(11) Ir1 - O41 - C42 - O43 = 17100(7) Ir1 - O41 - C42 - C44 = -1020(13) O43 - C42 - C44 - N49 = -11970(11) O41 - C42 - C44 - N49 = 6150(12) O43 - C42 - C44 - C45 = 590(15) O41 - C42 - C44 - C45 = -17290(10) N49 - C44 - C45 - C46 = -16850(10) C42 - C44 - C45 - C46 = 6800(14) C44 - C45 - C46 - C48 = 16930(11) C44 - C45 - C46 - C47 = 4830(15) C42 - C44 - N49 - C50 = 11590(12) C45 - C44 - N49 - C50 = -1220(15) C42 - C44 - N49 - C53 = -6640(13) C45 - C44 - N49 - C53 = 16550(10) C53 - N49 - C50 - C51 = -130(13) C44 - N49 - C50 - C51 = 17660(10) N49 - C50 - C51 - N52 = 280(13) C50 - C51 - N52 - C53 = -350(14) C50 - C51 - N52 - C54 = -17840(10) C51 - N52 - C53 - N49 = 250(13) C54 - N52 - C53 - N49 = 17710(10) C51 - N52 - C53 - Ir1 = 16680(10) C54 - N52 - C53 - Ir1 = -1860(19) C50 - N49 - C53 - N52 = -070(13) C44 - N49 - C53 - N52 = -17880(10) C50 - N49 - C53 - Ir1 = -16800(8) C44 - N49 - C53 - Ir1 = 1400(15) C53 - N52 - C54 - C59 = 10670(14) C51 - N52 - C54 - C59 = -7920(14) C53 - N52 - C54 - C55 = -7470(15) C51 - N52 - C54 - C55 = 9940(13) C59 - C54 - C55 - C56 = -290(17) N52 - C54 - C55 - C56 = 17850(10) C59 - C54 - C55 - C60 = 17360(11) N52 - C54 - C55 - C60 = -500(16) C54 - C55 - C56 - C57 = 050(17) C60 - C55 - C56 - C57 = -17610(11) C55 - C56 - C57 - C58 = 300(18) C55 - C56 - C57 - C61 = -17640(12) C56 - C57 - C58 - C59 = -420(19) C61 - C57 - C58 - C59 = 17500(13) C55 - C54 - C59 - C58 = 170(19)

S49

N52 - C54 - C59 - C58 = -17980(11) C55 - C54 - C59 - C62 = -17650(11) N52 - C54 - C59 - C62 = 210(18) C57 - C58 - C59 - C54 = 200(19) C57 - C58 - C59 - C62 = -17980(12)

X-ray crystallographic study of D(S)-4

bull ORTEP of D(S)-4 CCDC ndeg 1894795

(C40 H39 Ir N4 O2 H2 O) M = 81797 D8 VENTURE Bruker AXS diffractometer [] Mo-Kα radiation (λ =

071073 Aring) T = 150(2) K orthorhombic P 21 21 21 (IT19) a = 92852(6) b = 152175(12) c =

247997(19) Aring V = 35041(4) Aring3 Z = 4 d = 1550 gcm-3 μ = 3854 mm-1 The structure was solved by

dual-space algorithm using the SHELXT program [1] and then refined with full-matrix least-square


displacement parameters Except XXX linked hydrogen atoms that were introduced in the structural

model through Fourier difference maps analysis H atoms were finally included in their calculated

positions A final refinement on F2 with 8014 unique intensities and 414 parameters converged at ωR(F2)

= 00539 (R(F) = 00346) for 6874 observed reflections with I gt 2σ(I)



S50


Atom x y z occ U(eq) Ir1 041683(3) 034698(2) 065537(2) 1 001136(6) N1 05946(6) 03256(3) 060868(18) 1 00150(12) C2 07190(7) 02896(5) 06260(3) 1 00203(17) H2 0727431 0272863 0662748 1 0024 C3 08337(8) 02763(5) 05922(3) 1 00262(19) H3 0919858 0250712 0605607 1 0031 C4 08236(8) 03003(5) 05381(3) 1 00284(19) H4 0902515 0292077 0514297 1 0034 C5 06967(7) 03363(6) 05201(3) 1 00238(18) H5 0687026 0352152 0483229 1 0029 C6 05821(8) 03497(5) 05555(2) 1 00180(12) C7 04403(7) 03859(5) 05417(3) 1 00205(7) C8 04029(9) 04118(4) 04891(3) 1 00205(7) H8 0472733 0410152 0461080 1 0025 C9 02652(7) 04395(5) 04782(3) 1 00205(7) H9 0239066 0457012 0442801 1 0025 C10 01648(8) 04416(5) 05195(3) 1 00205(7) H10 0069297 0460242 0511856 1 0025 C11 02003(8) 04171(5) 05715(3) 1 00205(7) H11 0128245 0418099 0598649 1 0025 C12 03414(8) 03906(5) 05850(3) 1 00205(7) N13 02233(5) 03619(4) 06940(2) 1 00137(13) C14 01752(7) 04380(5) 07157(3) 1 00177(16) H14 0232727 0489343 0712350 1 0021 C15 00464(7) 04434(6) 07424(3) 1 0026(2) H15 0013807 0497942 0756501 1 0031 C16 -00354(8) 03683(6) 07483(3) 1 0032(2) H16 -0122823 0370097 0768154 1 0039 C17 00100(8) 02914(6) 07255(3) 1 00275(19) H17 -0046445 0239719 0729425 1 0033 C18 01392(7) 02883(5) 06965(3) 1 00186(17) C19 01932(7) 02136(5) 06663(3) 1 00162(16) C20 01194(7) 01340(5) 06621(3) 1 00243(18) H20 0030921 0126063 0680681 1 0029 C21 01740(9) 00671(5) 06312(3) 1 00284(19) H21 0123388 0013041 0628206 1 0034 C22 03033(9) 00787(5) 06044(3) 1 0027(2) H22 0342153 0032161 0583434 1 0032 C23 03773(7) 01587(6) 06080(2) 1 00212(16) H23 0465321 0165716 0588924 1 0025 C24 03249(7) 02279(5) 06388(2) 1 00150(16) O25 05182(5) 02796(3) 072311(18) 1 00182(11) C26 05811(8) 03114(4) 07637(2) 1 00152(14) O27 06768(5) 02713(3) 078928(19) 1 00205(12) C28 05394(7) 04016(5) 07853(3) 1 00138(16) H28 0614478 0418929 0812123 1 0017 C28B 03971(8) 03946(5) 08156(3) 1 00214(17) H00A 0322102 0373919 0790209 1 0026 H00B 0368920 0453998 0827964 1 0026 C29 03993(8) 03329(5) 08644(2) 1 00211(16) H29 0440046 0275517 0852119 1 0025 C30 02475(9) 03157(6) 08842(3) 1 0043(2) H30A 0202776 0371234 0895079 1 0064 H30B 0250571 0275604 0915093 1 0064 H30C 0190855 0288981 0855119 1 0064 C31 04932(8) 03657(6) 09105(3) 1 0031(2) H31A 0456862 0422477 0923199 1 0046 H31B 0592536 0372619 0897748 1 0046 H31C 0490874 0323124 0940092 1 0046 N32 05375(5) 04705(4) 07429(2) 1 00130(12) C33 05868(8) 05536(4) 07549(2) 1 00185(14) H33 0616848 0574389 0789191 1 0022 C34 05843(9) 05993(4) 07089(2) 1 00204(15) H34 0610416 0659230 0704569 1 0024 N35 05367(5) 05432(4) 066886(19) 1 00136(13) C36 05040(6) 04616(5) 06890(3) 1 00131(15) C37 05458(7) 05683(5) 06123(3) 1 00154(16) C38 06801(7) 05595(5) 05874(3) 1 00192(16) C39 06933(7) 05904(5) 05349(3) 1 00217(17) H39 0783491 0585191 0517065 1 0026 C40 05790(9) 06285(4) 05078(2) 1 00217(15)

S51

C41 04484(7) 06361(4) 05341(3) 1 00172(16) H41 0369898 0662511 0515636 1 0021 C42 04270(9) 06065(4) 05870(2) 1 00166(14) C43 08087(7) 05230(6) 06166(3) 1 0029(2) H43A 0838873 0564298 0644728 1 0043 H43B 0887797 0514297 0590995 1 0043 H43C 0783159 0466602 0633099 1 0043 C44 05995(9) 06643(6) 04511(2) 1 0034(2) H44A 0701355 0678199 0445335 1 0051 H44B 0541615 0717635 0446603 1 0051 H44C 0568646 0620040 0424799 1 0051 C45 02864(7) 06192(5) 06152(3) 1 00214(18) H45A 0266151 0567888 0637819 1 0032 H45B 0209529 0626026 0588402 1 0032 H45C 0291175 0671937 0637758 1 0032 O101 07609(6) 01253(4) 07302(2) 1 00336(14) H1W 0740(8) 0172(4) 0751(3) 1 0050 H2W 0688(6) 0121(6) 0707(3) 1 0050



Atom U11 U22 U33 U23 U13 U12 Ir1 001418(10) 000967(11) 001022(10) -000041(12) -000057(12) 000032(13) N1 0021(3) 0012(3) 0011(2) -0003(2) 0003(3) -0003(3) C2 0022(4) 0024(5) 0015(4) 0001(3) -0003(3) 0006(3) C3 0021(4) 0024(5) 0033(5) -0003(4) 0003(3) 0010(3) C4 0034(4) 0022(5) 0030(4) -0004(4) 0010(4) 0011(4) C5 0033(4) 0026(5) 0012(3) 0009(4) 0008(3) 0006(4) C6 0026(3) 0016(3) 0012(3) -0002(3) 0001(3) 0002(5) C7 00295(17) 00159(17) 00161(15) 00014(13) -00054(13) 00017(14) C8 00295(17) 00159(17) 00161(15) 00014(13) -00054(13) 00017(14) C9 00295(17) 00159(17) 00161(15) 00014(13) -00054(13) 00017(14) C10 00295(17) 00159(17) 00161(15) 00014(13) -00054(13) 00017(14) C11 00295(17) 00159(17) 00161(15) 00014(13) -00054(13) 00017(14) C12 00295(17) 00159(17) 00161(15) 00014(13) -00054(13) 00017(14) N13 0017(3) 0011(4) 0013(3) 0000(2) 0002(2) -0002(2) C14 0016(4) 0015(4) 0022(4) 0001(3) -0001(3) -0001(3) C15 0021(4) 0026(5) 0030(4) -0011(4) 0003(3) 0004(4) C16 0018(4) 0041(7) 0037(5) -0012(4) 0007(3) -0007(4) C17 0025(4) 0021(5) 0036(5) 0001(4) 0004(4) -0007(3) C18 0015(3) 0022(5) 0019(4) 0001(3) -0007(3) -0004(3) C19 0020(3) 0012(4) 0016(4) 0001(3) -0007(3) -0004(3) C20 0028(4) 0020(5) 0025(4) 0007(3) -0012(3) -0005(3) C21 0042(5) 0016(5) 0028(4) 0000(4) -0022(4) -0009(4) C22 0053(5) 0010(4) 0017(4) -0005(3) -0019(4) 0007(4) C23 0034(4) 0015(4) 0015(3) 0000(4) -0007(3) 0000(4) C24 0027(4) 0006(4) 0012(4) 0000(3) -0014(3) 0004(3) O25 0028(3) 0014(3) 0013(2) 0003(2) -0007(2) 0001(2) C26 0014(3) 0016(4) 0016(3) 0009(3) 0007(4) -0003(4) O27 0020(3) 0019(3) 0023(3) 0003(2) -0004(2) -0001(2) C28 0020(4) 0013(4) 0009(3) 0002(3) -0001(3) -0001(3) C28B 0022(4) 0028(5) 0015(3) 0002(3) 0002(3) 0000(4) C29 0027(4) 0015(4) 0021(3) 0002(3) 0006(3) -0005(4) C30 0035(5) 0056(7) 0037(5) 0008(5) 0013(4) -0010(5) C31 0045(5) 0025(6) 0024(4) 0006(4) 0001(3) -0001(4) N32 0019(3) 0010(3) 0010(3) 0003(2) -0004(2) -0001(2) C33 0026(3) 0013(4) 0017(3) -0001(3) -0009(4) 0000(4) C34 0027(4) 0008(4) 0026(4) -0003(3) -0007(4) -0007(4) N35 0018(3) 0010(3) 0014(3) 0003(2) -0003(2) 0000(2) C36 0010(3) 0011(4) 0018(4) -0003(3) 0005(3) 0001(3) C37 0028(4) 0005(4) 0013(3) 0000(3) 0001(3) -0005(3) C38 0028(4) 0012(4) 0017(4) -0004(3) -0003(3) -0001(3) C39 0022(4) 0021(5) 0022(4) 0000(3) 0003(3) -0001(3) C40 0033(4) 0017(4) 0015(3) 0003(3) -0002(4) -0003(4) C41 0027(4) 0008(4) 0017(3) 0002(3) -0008(3) 0002(3) C42 0025(4) 0010(4) 0015(3) -0002(3) -0006(3) -0002(4) C43 0026(4) 0032(5) 0028(4) 0000(4) 0000(3) 0006(4) C44 0036(4) 0047(6) 0020(4) 0010(4) -0002(3) 0008(5)

S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)


Ir1 - C12 = 1994(7) Ir1 - N1 = 2042(5) Ir1 - C24 = 2044(7) Ir1 - N13 = 2049(5) Ir1 - C36 = 2097(7) Ir1 - O25 = 2181(4) N1 - C2 = 1349(8) N1 - C6 = 1374(7) C2 - C3 = 1369(9) C2 - H2 = 09500 C3 - C4 = 1393(10) C3 - H3 = 09500 C4 - C5 = 1373(9) C4 - H4 = 09500 C5 - C6 = 1395(9) C5 - H5 = 09500 C6 - C7 = 1468(10) C7 - C8 = 1406(8) C7 - C12 = 1416(9) C8 - C9 = 1372(10) C8 - H8 = 09500 C9 - C10 = 1384(9) C9 - H9 = 09500 C10 - C11 = 1382(9) C10 - H10 = 09500 C11 - C12 = 1411(10) C11 - H11 = 09500 N13 - C14 = 1353(9) N13 - C18 = 1367(9) C14 - C15 = 1370(9) C14 - H14 = 09500 C15 - C16 = 1380(10) C15 - H15 = 09500 C16 - C17 = 1366(11) C16 - H16 = 09500 C17 - C18 = 1400(9) C17 - H17 = 09500 C18 - C19 = 1450(10) C19 - C20 = 1397(9) C19 - C24 = 1418(9) C20 - C21 = 1371(10) C20 - H20 = 09500 C21 - C22 = 1384(11) C21 - H21 = 09500 C22 - C23 = 1400(11) C22 - H22 = 09500 C23 - C24 = 1390(10) C23 - H23 = 09500 O25 - C26 = 1260(8) C26 - O27 = 1251(8) C26 - C28 = 1523(9) C28 - N32 = 1484(8) C28 - C28B = 1524(9) C28 - H28 = 10000 C28B - C29 = 1532(9) C28B - H00A = 09900 C28B - H00B = 09900 C29 - C30 = 1516(10) C29 - C31 = 1521(9) C29 - H29 = 10000 C30 - H30A = 09800 C30 - H30B = 09800 C30 - H30C = 09800 C31 - H31A = 09800 C31 - H31B = 09800 C31 - H31C = 09800 N32 - C36 = 1378(8) N32 - C33 = 1378(8) C33 - C34 = 1335(8) C33 - H33 = 09500

S53

C34 - N35 = 1382(8) C34 - H34 = 09500 N35 - C36 = 1372(9) N35 - C37 = 1455(8) C37 - C42 = 1397(9) C37 - C38 = 1398(9) C38 - C39 = 1390(10) C38 - C43 = 1503(9) C39 - C40 = 1384(9) C39 - H39 = 09500 C40 - C41 = 1383(10) C40 - C44 = 1519(8) C41 - C42 = 1399(8) C41 - H41 = 09500 C42 - C45 = 1494(10) C43 - H43A = 09800 C43 - H43B = 09800 C43 - H43C = 09800 C44 - H44A = 09800 C44 - H44B = 09800 C44 - H44C = 09800 C45 - H45A = 09800 C45 - H45B = 09800 C45 - H45C = 09800 O101 - H1W = 090(3) O101 - H2W = 089(3)

Angles [deg]

C12 - Ir1 - N1 = 8080(3) C12 - Ir1 - C24 = 8840(3) N1 - Ir1 - C24 = 9470(2) C12 - Ir1 - N13 = 9370(3) N1 - Ir1 - N13 = 17250(2) C24 - Ir1 - N13 = 8000(3) C12 - Ir1 - C36 = 10190(3) N1 - Ir1 - C36 = 9260(2) C24 - Ir1 - C36 = 16820(2) N13 - Ir1 - C36 = 9350(2) C12 - Ir1 - O25 = 16910(2) N1 - Ir1 - O25 = 9075(19) C24 - Ir1 - O25 = 8540(2) N13 - Ir1 - O25 = 9405(19) C36 - Ir1 - O25 = 8530(2) C2 - N1 - C6 = 11910(6) C2 - N1 - Ir1 = 12520(4) C6 - N1 - Ir1 = 11570(5) N1 - C2 - C3 = 12210(6) N1 - C2 - H2 = 11900 C3 - C2 - H2 = 11900 C2 - C3 - C4 = 11980(7) C2 - C3 - H3 = 12010 C4 - C3 - H3 = 12010 C5 - C4 - C3 = 11840(7) C5 - C4 - H4 = 12080 C3 - C4 - H4 = 12080 C4 - C5 - C6 = 12050(6) C4 - C5 - H5 = 11970 C6 - C5 - H5 = 11970 N1 - C6 - C5 = 12000(6) N1 - C6 - C7 = 11360(6) C5 - C6 - C7 = 12630(5) C8 - C7 - C12 = 12200(7) C8 - C7 - C6 = 12290(6) C12 - C7 - C6 = 11500(6) C9 - C8 - C7 = 11980(7) C9 - C8 - H8 = 12010 C7 - C8 - H8 = 12010 C8 - C9 - C10 = 11940(6) C8 - C9 - H9 = 12030 C10 - C9 - H9 = 12030 C11 - C10 - C9 = 12150(7) C11 - C10 - H10 = 11930 C9 - C10 - H10 = 11930 C10 - C11 - C12 = 12140(7)

S54

C10 - C11 - H11 = 11930 C12 - C11 - H11 = 11930 C11 - C12 - C7 = 11580(6) C11 - C12 - Ir1 = 12900(5) C7 - C12 - Ir1 = 11480(5) C14 - N13 - C18 = 11960(6) C14 - N13 - Ir1 = 12480(5) C18 - N13 - Ir1 = 11560(5) N13 - C14 - C15 = 12220(7) N13 - C14 - H14 = 11890 C15 - C14 - H14 = 11890 C14 - C15 - C16 = 11880(7) C14 - C15 - H15 = 12060 C16 - C15 - H15 = 12060 C17 - C16 - C15 = 11970(7) C17 - C16 - H16 = 12010 C15 - C16 - H16 = 12010 C16 - C17 - C18 = 12040(8) C16 - C17 - H17 = 11980 C18 - C17 - H17 = 11980 N13 - C18 - C17 = 11910(7) N13 - C18 - C19 = 11490(6) C17 - C18 - C19 = 12600(7) C20 - C19 - C24 = 12130(7) C20 - C19 - C18 = 12340(6) C24 - C19 - C18 = 11530(6) C21 - C20 - C19 = 12040(7) C21 - C20 - H20 = 11980 C19 - C20 - H20 = 11980 C20 - C21 - C22 = 11960(7) C20 - C21 - H21 = 12020 C22 - C21 - H21 = 12020 C21 - C22 - C23 = 12050(7) C21 - C22 - H22 = 11980 C23 - C22 - H22 = 11980 C24 - C23 - C22 = 12150(7) C24 - C23 - H23 = 11930 C22 - C23 - H23 = 11930 C23 - C24 - C19 = 11680(6) C23 - C24 - Ir1 = 12960(5) C19 - C24 - Ir1 = 11350(5) C26 - O25 - Ir1 = 12940(4) O27 - C26 - O25 = 12310(6) O27 - C26 - C28 = 11630(6) O25 - C26 - C28 = 12050(6) N32 - C28 - C26 = 11300(5) N32 - C28 - C28B = 11290(5) C26 - C28 - C28B = 10930(6) N32 - C28 - H28 = 10710 C26 - C28 - H28 = 10710 C28B - C28 - H28 = 10710 C28 - C28B - C29 = 11490(6) C28 - C28B - H00A = 10850 C29 - C28B - H00A = 10850 C28 - C28B - H00B = 10850 C29 - C28B - H00B = 10850 H00A - C28B - H00B = 10750 C30 - C29 - C31 = 11040(6) C30 - C29 - C28B = 11040(6) C31 - C29 - C28B = 11360(6) C30 - C29 - H29 = 10740 C31 - C29 - H29 = 10740 C28B - C29 - H29 = 10740 C29 - C30 - H30A = 10950 C29 - C30 - H30B = 10950 H30A - C30 - H30B = 10950 C29 - C30 - H30C = 10950 H30A - C30 - H30C = 10950 H30B - C30 - H30C = 10950 C29 - C31 - H31A = 10950 C29 - C31 - H31B = 10950 H31A - C31 - H31B = 10950 C29 - C31 - H31C = 10950 H31A - C31 - H31C = 10950 H31B - C31 - H31C = 10950 C36 - N32 - C33 = 11190(5) C36 - N32 - C28 = 12840(6)

S55

C33 - N32 - C28 = 11940(5) C34 - C33 - N32 = 10670(5) C34 - C33 - H33 = 12660 N32 - C33 - H33 = 12660 C33 - C34 - N35 = 10730(6) C33 - C34 - H34 = 12630 N35 - C34 - H34 = 12630 C36 - N35 - C34 = 11160(5) C36 - N35 - C37 = 12700(6) C34 - N35 - C37 = 12080(6) N35 - C36 - N32 = 10240(6) N35 - C36 - Ir1 = 13390(5) N32 - C36 - Ir1 = 12360(5) C42 - C37 - C38 = 12300(6) C42 - C37 - N35 = 11980(6) C38 - C37 - N35 = 11690(6) C39 - C38 - C37 = 11750(6) C39 - C38 - C43 = 12040(6) C37 - C38 - C43 = 12200(6) C40 - C39 - C38 = 12190(7) C40 - C39 - H39 = 11900 C38 - C39 - H39 = 11900 C41 - C40 - C39 = 11860(6) C41 - C40 - C44 = 12120(7) C39 - C40 - C44 = 12020(7) C40 - C41 - C42 = 12270(6) C40 - C41 - H41 = 11870 C42 - C41 - H41 = 11870 C37 - C42 - C41 = 11630(7) C37 - C42 - C45 = 12220(6) C41 - C42 - C45 = 12140(6) C38 - C43 - H43A = 10950 C38 - C43 - H43B = 10950 H43A - C43 - H43B = 10950 C38 - C43 - H43C = 10950 H43A - C43 - H43C = 10950 H43B - C43 - H43C = 10950 C40 - C44 - H44A = 10950 C40 - C44 - H44B = 10950 H44A - C44 - H44B = 10950 C40 - C44 - H44C = 10950 H44A - C44 - H44C = 10950 H44B - C44 - H44C = 10950 C42 - C45 - H45A = 10950 C42 - C45 - H45B = 10950 H45A - C45 - H45B = 10950 C42 - C45 - H45C = 10950 H45A - C45 - H45C = 10950 H45B - C45 - H45C = 10950 H1W - O101 - H2W = 10500(6)

Torsion angles [deg] C6 - N1 - C2 - C3 = 010(11) Ir1 - N1 - C2 - C3 = 17930(6) N1 - C2 - C3 - C4 = 000(12) C2 - C3 - C4 - C5 = -060(12) C3 - C4 - C5 - C6 = 110(12) C2 - N1 - C6 - C5 = 040(10) Ir1 - N1 - C6 - C5 = -17890(6) C2 - N1 - C6 - C7 = 17850(6) Ir1 - N1 - C6 - C7 = -080(8) C4 - C5 - C6 - N1 = -110(12) C4 - C5 - C6 - C7 = -17890(8) N1 - C6 - C7 - C8 = -17770(6) C5 - C6 - C7 - C8 = 020(12) N1 - C6 - C7 - C12 = 050(9) C5 - C6 - C7 - C12 = 17840(7) C12 - C7 - C8 - C9 = -260(11) C6 - C7 - C8 - C9 = 17550(7) C7 - C8 - C9 - C10 = 010(11) C8 - C9 - C10 - C11 = 050(11) C9 - C10 - C11 - C12 = 130(12) C10 - C11 - C12 - C7 = -360(11) C10 - C11 - C12 - Ir1 = -17660(6) C8 - C7 - C12 - C11 = 420(11) C6 - C7 - C12 - C11 = -17400(7)

S56

C8 - C7 - C12 - Ir1 = 17820(6) C6 - C7 - C12 - Ir1 = 000(8) C18 - N13 - C14 - C15 = 270(10) Ir1 - N13 - C14 - C15 = -17820(5) N13 - C14 - C15 - C16 = 150(11) C14 - C15 - C16 - C17 = -300(11) C15 - C16 - C17 - C18 = 030(12) C14 - N13 - C18 - C17 = -540(10) Ir1 - N13 - C18 - C17 = 17540(5) C14 - N13 - C18 - C19 = 17280(6) Ir1 - N13 - C18 - C19 = -640(7) C16 - C17 - C18 - N13 = 390(11) C16 - C17 - C18 - C19 = -17410(7) N13 - C18 - C19 - C20 = -17720(6) C17 - C18 - C19 - C20 = 090(11) N13 - C18 - C19 - C24 = 000(9) C17 - C18 - C19 - C24 = 17800(6) C24 - C19 - C20 - C21 = 050(10) C18 - C19 - C20 - C21 = 17750(6) C19 - C20 - C21 - C22 = 030(11) C20 - C21 - C22 - C23 = -100(11) C21 - C22 - C23 - C24 = 080(11) C22 - C23 - C24 - C19 = 000(9) C22 - C23 - C24 - Ir1 = 17500(5) C20 - C19 - C24 - C23 = -070(9) C18 - C19 - C24 - C23 = -17790(6) C20 - C19 - C24 - Ir1 = -17650(5) C18 - C19 - C24 - Ir1 = 630(7) Ir1 - O25 - C26 - O27 = -15360(5) Ir1 - O25 - C26 - C28 = 2830(9) O27 - C26 - C28 - N32 = 13080(6) O25 - C26 - C28 - N32 = -5100(8) O27 - C26 - C28 - C28B = -10260(7) O25 - C26 - C28 - C28B = 7560(7) N32 - C28 - C28B - C29 = -17250(6) C26 - C28 - C28B - C29 = 6080(7) C28 - C28B - C29 - C30 = -16790(6) C28 - C28B - C29 - C31 = 6750(8) C26 - C28 - N32 - C36 = 3190(9) C28B - C28 - N32 - C36 = -9270(7) C26 - C28 - N32 - C33 = -14140(7) C28B - C28 - N32 - C33 = 9390(7) C36 - N32 - C33 - C34 = 050(8) C28 - N32 - C33 - C34 = 17490(6) N32 - C33 - C34 - N35 = -140(9) C33 - C34 - N35 - C36 = 190(9) C33 - C34 - N35 - C37 = -16910(6) C34 - N35 - C36 - N32 = -150(7) C37 - N35 - C36 - N32 = 16880(5) C34 - N35 - C36 - Ir1 = 17590(5) C37 - N35 - C36 - Ir1 = -1380(9) C33 - N32 - C36 - N35 = 060(7) C28 - N32 - C36 - N35 = -17320(5) C33 - N32 - C36 - Ir1 = -17720(5) C28 - N32 - C36 - Ir1 = 910(8) C36 - N35 - C37 - C42 = 9550(8) C34 - N35 - C37 - C42 = -9500(8) C36 - N35 - C37 - C38 = -9000(8) C34 - N35 - C37 - C38 = 7950(8) C42 - C37 - C38 - C39 = -030(11) N35 - C37 - C38 - C39 = -17450(6) C42 - C37 - C38 - C43 = 17630(7) N35 - C37 - C38 - C43 = 210(10) C37 - C38 - C39 - C40 = 000(11) C43 - C38 - C39 - C40 = -17670(7) C38 - C39 - C40 - C41 = 030(11) C38 - C39 - C40 - C44 = 17790(7) C39 - C40 - C41 - C42 = -030(10) C44 - C40 - C41 - C42 = -17790(7) C38 - C37 - C42 - C41 = 020(10) N35 - C37 - C42 - C41 = 17440(6) C38 - C37 - C42 - C45 = -17710(6) N35 - C37 - C42 - C45 = -290(10) C40 - C41 - C42 - C37 = 000(10) C40 - C41 - C42 - C45 = 17730(6)

S57

9 Computational details

All calculations were carried out with the Gaussian 09 package6 and the B3LYP hybrid

functional[7] on the real experimental systems The iridium atom was described with the relativistic

electron core potential SDD and associated basis set8 augmented by a set of f-orbital polarization

functions9 The 6-31G basis set were employed for all other atoms Optimizations were carried out without any symmetry restrictions taking into solvent effect (DCM CH2Cl2) by means of the universal

Solvation Model based on solute electron Density10 All stationary points involved were fully optimized

Frequency calculations were realized to confirm the nature of the minima (positive frequencies) CD and

VCD spectra were computed for all relevant diastereomers Time-Dependent Density Functional Theory

(TD-DFT) calculations have been performed to obtain ECD spectra The same level of theory was

adopted and 60 excited states were admitted VCD spectra were generated with Gaussview 6011 by

assigning 4 cmminus1 bandwidth Lorentzian band shape to each vibrational transition and plotted with excel

Energies have been scaled by a factor of 098 to directly compare with the experimental spectra

[6] Gaussian 09 Revision C01 M J Frisch G W Trucks H B Schlegel G E Scuseria M A Robb J R Cheeseman G

Scalmani V Barone B Mennucci G A Petersson H Nakatsuji M Caricato X Li H P Hratchian A F Izmaylov J Bloino G Zheng J L Sonnenberg M Hada M Ehara K Toyota R Fukuda J Hasegawa M Ishida T Nakajima Y Honda O Kitao H Nakai T Vreven J A Montgomery Jr J E Peralta F Ogliaro M Bearpark J J Heyd E Brothers K N Kudin V N Staroverov T Keith R Kobayashi J Normand K Raghavachari A Rendell J C Burant S S Iyengar J Tomasi M Cossi N Rega J M Millam M Klene J E Knox J B Cross V Bakken C Adamo J Jaramillo R Gomperts R E Stratmann O Yazyev A J Austin R Cammi C Pomelli J W Ochterski R L Martin K Morokuma V G Zakrzewski G A Voth P Salvador J J Dannenberg S Dapprich A D Daniels O Farkas J B Foresman J V Ortiz J Cioslowski and D J Fox Gaussian Inc Wallingford CT 2009

[7] a) A D Becke J Chem Phys 1993 98 5648 b) C Lee W Yang R G Parr Phys Rev B 1988 37 785 [8] a) D Andrae U Haumlussermann M Dolg H Stoll H Preuss Theor Chim Acta 1990 77 123 b) M Dolg Modern Methods

and Algorithm of Quantum Chemistry Vol 1 (Ed J Grotendorst) John von Neuman Institute for Computing Juumllich (Germany) 2000 479

[9] A W Ehlers M Biihme S Dapprich A Gobbi A Hijllwarth V Jonas K F Kiihler R Stegmann A Veldkamp G Frenking Chem Phys Letters 1993 208 111

[10] A V Marenich C J Cramer D G Truhlar J Phys Chem B 2009 113 6378 [11] GaussView Version 6 R Dennington T- A Keith J- M Millam Semichem Inc Shawnee Mission KS 2016

S58

In agreement with experimental data L(S)-3 was found slightly lower in energy than D(S)-4 (DG about 12 kcalmol) In the same way D(R)-3 was found slightly lower in energy than L(R)-4 (DG around 06 kcalmol)

Figure S33 Structures of the different diastereomers optimized at SMD(DCM)-B3LYPSDD+f(Ir) 6-

31G(other atoms) level of theory

Ir O

N

CO

S59

Z-matrices (energies in au)

L-(R)-4 Sum of electronic and zero-point Energies= -2021142914 Sum of electronic and thermal Energies= -2021100324 Sum of electronic and thermal Enthalpies= -2021099380 Sum of electronic and thermal Free Energies= -2021218048 Ir 035915400 050821000 -017876100 N 155108400 039515300 153301000 C 162880800 -066885500 236009400 H 104157500 -153108800 207763700 C 241149700 -068239700 350513000 H 242960700 -156758700 413094200 C 316431400 045231500 381196500 H 379624000 047856400 469427700 C 308792600 155385100 297162100 H 365371400 244998100 319593500 C 226519400 152537700 183588400 C 206165900 264832600 091566000 C 274143600 387315200 103988300 H 347609000 402304300 182601800 C 248195400 490764700 014623800 H 300822500 585330700 023897300 C 153807900 471716200 -086876600 H 132811600 552203600 -156959900 C 086592400 349767400 -099150100 H 014611600 338440100 -179780500 C 110654500 242716200 -011228600 N -086551400 092777600 -179428800 C -051072200 076136300 -308574400 H 047580200 034745400 -325273900 C -134481100 111614300 -413574300 H -101392800 096304000 -515686700 C -259460800 166829200 -384262300 H -327276600 195743500 -463956400 C -295812200 184959000 -251552900 H -391928400 228419100 -226786000 C -208057400 147845200 -148564800 C -232099800 164078400 -005172600 C -348444000 222940400 047466800 H -427574600 257089300 -018691200 C -362912000 239037500 184867000 H -452515200 285109100 225418700 C -260419500 195827100 269982800 H -270541400 208682800 377526100 C -145049700 136723200 218207000 H -067426600 104943500 287232700 C -127061000 118163500 079672700 O 276988400 -114724800 -325048300 C 237163400 -102064400 -208401700 O 205398800 009779800 -153658100 C 229044300 -229350000 -121379600 H 248419800 -312787500 -188996900 C 474003200 -280568700 -046066600 H 464107400 -373330200 -104477500 C 548766500 -177858900 -132374400 H 497291400 -158589100 -226809000 H 649778000 -213438800 -155758900 H 558803700 -082317000 -079285800 C 554749400 -313355300 080459900 H 565637600 -224690300 144161400 H 655431000 -348320200 055035400 H 506306600 -391509300 140129600 N 090730500 -253103400 -072628000 C 042413400 -383254900 -069906000 H 102962500 -467315300 -099989400 C -085269300 -376724100 -026541500 H -159458900 -453442000 -011129900 N -112811500 -242290800 -003115000 C -003626900 -162654000 -030586900 C -247224900 -204402000 034503100 C -282841000 -201590100 170470400 C -416630300 -176605700 202806500

S60

H -445220300 -173915700 307678000 C -514249700 -156573500 104597200 C -475577600 -164133700 -029561700 H -550496100 -151774500 -107383000 C -343127400 -189141000 -067235300 C -182109000 -226331700 279915400 H -120081700 -314101000 259111400 H -232699100 -242503500 375465600 H -115059600 -140710000 292017100 C -657103000 -126390300 142702300 H -726361300 -152049500 062004400 H -669965000 -019560000 164274200 H -687130200 -181210900 232563700 C -307847300 -204691600 -213132500 H -217919500 -148916000 -240130400 H -389920600 -169955400 -276361900 H -288971300 -309827400 -238094700 C 331892700 -235200200 -006054300 H 293175300 -306585000 067653800 H 337219500 -137833300 043498200

L-(S)-3 Sum of electronic and zero-point Energies= -2021147314 Sum of electronic and thermal Energies= -2021104779 Sum of electronic and thermal Enthalpies= -2021103835 Sum of electronic and thermal Free Energies= -2021222040 Ir -030101700 057167200 020947800 N -160954900 081410800 -140318900 C -178750500 -007899100 -240183900 H -121772200 -099583100 -232377700 C -264340200 014197200 -346983500 H -274395300 -061313400 -424136900 C -335857500 134074700 -351386400 H -404441100 154867100 -432909800 C -317074300 227144600 -250228100 H -370133600 321543100 -252780400 C -227901900 200872100 -145078900 C -194373100 294639200 -037438300 C -255623200 420501400 -023735300 H -334001100 451944200 -092056600 C -216400800 506365400 078496200 H -263775700 603516500 089246500 C -115665800 466336200 166920800 H -084276000 533048600 246890900 C -055374200 340932200 153544800 H 021851700 313043000 224745400 C -092719700 251149400 051984600 N 106534300 065873900 175691500 C 078905600 032222100 303395600 H -021160900 -005696100 320320100 C 171335500 047563300 405669500 H 144343600 019430900 506846100 C 297538500 099104500 374816500 H 372482000 112087000 452288200 C 326056900 134011200 243509300 H 423160900 174540400 217620300 C 228978800 117880100 143511700 C 243873300 153649500 002421100 C 360575700 211410200 -050580700 H 446151800 231046000 013417900 C 367277100 244852500 -185434400 H 457341300 289804300 -226221000 C 256590700 220361100 -267622800 H 260830800 246596900 -373103200 C 140405100 163157400 -215446800 H 056411000 146203300 -282192900 C 130000000 127518800 -079529300 O -187248400 000677900 168588800 C -248261500 -112704300 175125600 O -300812000 -159326900 276751100 C -252027700 -192518200 042056900 H -275648300 -121655400 -037213200 C -501289500 -257418000 046918100 H -510902500 -191775000 134182300

S61

C -542945300 -178541100 -078089100 H -484736400 -086722900 -090936600 H -648343800 -149226900 -071843200 H -530791700 -238991000 -168919500 C -594585200 -377547100 067886000 H -588102200 -448154800 -015926200 H -699013300 -345308300 075738300 H -569609500 -432290600 159469300 N -113966200 -240670600 014705500 C -077005900 -374263300 008012300 H -146584700 -455307600 021077800 C 055944200 -376447900 -016679300 H 124326700 -458706000 -030343700 N 098074700 -243958800 -023629200 C -006535400 -157143200 -003468400 C 236695200 -214205200 -051110900 C 276537000 -191615600 -184180900 C 412675500 -172989400 -209677100 H 444605500 -155194700 -312086800 C 508610500 -178173700 -107763100 C 465369600 -204425700 022472600 H 538501200 -211098000 102651200 C 330115700 -224135600 053284200 C 176970300 -190878100 -297407100 H 117847600 -283145100 -299381300 H 228298200 -181643500 -393449500 H 106971800 -107300400 -288703900 C 654564600 -155332700 -138517300 H 718307000 -184926000 -054721500 H 674072200 -049406800 -159349100 H 686093100 -211634800 -227017900 C 289299100 -259814900 194105400 H 199454100 -206524000 225869000 H 369674000 -236509200 264374900 H 267834200 -367009600 203124200 C -354718800 -305765600 041283000 H -335969900 -370696400 127402600 H -341616200 -365869600 -049666200

D-(R)-3 Sum of electronic and zero-point Energies= -2021145205 Sum of electronic and thermal Energies= -2021102864 Sum of electronic and thermal Enthalpies= -2021101920 Sum of electronic and thermal Free Energies= -2021219037 Ir 026821700 069974900 023245600 N -122437500 081553300 165787600 C -102171500 066047100 298262200 H -000654600 040834200 326465300 C -203579300 083538900 391246000 H -182340900 070322700 496750800 C -331105200 118077400 345619500 H -412881100 132456400 415563200 C -352073000 134366300 209361700 H -450063600 161834900 172126200 C -246220400 116455400 119011700 C -252973300 133687800 -026122200 C -370130400 171727100 -093880600 H -462288000 188859900 -038970000 C -369064900 188460000 -231966900 H -459568400 218155300 -284152500 C -250059500 167023400 -302569500 H -248170000 180391200 -410508000 C -133458100 129231900 -235714200 H -042916500 114257700 -293805600 C -130698400 110727000 -096069400 N 167313400 090526800 -129999000 C 203114300 -007031600 -216340900 H 156436700 -103361800 -200597000 C 293841500 012653800 -319351300 H 318466800 -069616300 -385515600 C 351702500 138931000 -334058900 H 423954000 158103200 -412760100 C 314434900 240204300 -246912400 H 356669600 339395000 -257536400 C 220466900 215867800 -145555600

S62

C 168037600 316992100 -053282400 C 213263100 450158600 -052044500 H 292124600 482614300 -119334400 C 157234200 542010200 036162500 H 192158800 644851900 037302900 C 055715100 500546900 123041600 H 011310800 571803700 192190500 C 011144300 368074900 121832300 H -067384200 339547900 191323900 C 065610300 272240700 034534700 O 174734300 047456700 186699600 C 251722100 -053038900 211046300 O 309309700 -073379700 318346800 C 271700300 -151620400 092703400 N 140715400 -215852000 062121200 C 116460400 -352315500 070580000 H 190967700 -423939900 100342700 C -012648100 -371263200 035285100 H -071513400 -461227800 027083400 N -065648800 -245871000 006824900 C 028192200 -146870200 023948600 C -203099200 -234496200 -036047300 C -304921000 -241638800 060432500 C -437789600 -239822400 016004700 H -517461100 -244400900 089853100 C -470407700 -233868900 -119720200 C -365909300 -231473700 -212938200 H -389262500 -229755400 -319124800 C -231751800 -232703000 -173848900 C -274914300 -256672500 207579500 H -247168800 -360031900 231778600 H -362880200 -231743900 267413000 H -192272300 -192983600 239769600 C -614207800 -230091600 -165366300 H -682699800 -255267000 -083912600 H -631875600 -299999900 -247815900 H -641236000 -130202000 -201779400 C -122397500 -235905800 -277635000 H -064136300 -143344200 -277365000 H -164949500 -248232700 -377559400 H -052804000 -318690500 -260059100 C 384246000 -252086700 118589400 H 352959900 -322930700 195988100 H 465359800 -194657600 164456000 C 439801500 -326678100 -004891600 H 355843400 -361923000 -066403700 C 519792400 -449935800 039708000 H 457263900 -520426800 095701000 H 561709900 -503424500 -046257800 H 603321000 -421094900 104748900 C 526777600 -235056900 -092275300 H 472788300 -145668600 -125195000 H 615640000 -201797800 -037206200 H 561074600 -287570400 -182140000 H 297196800 -091034900 005566400

D-(S)-4 Sum of electronic and zero-point Energies= -2021145085 Sum of electronic and thermal Energies= -2021102448 Sum of electronic and thermal Enthalpies= -2021101504 Sum of electronic and thermal Free Energies= -2021220108 Ir 031348200 054955100 020065000 N -091949800 084244100 183516600 C -054773900 064168900 311660300 H 046165200 027613000 325791700 C -139234500 090630500 418427600 H -104720200 072968700 519684200 C -267306300 139981800 391949000 H -336147300 161581500 473066500 C -305478800 161593600 260274200 H -404111200 200330100 237642300 C -216382500 133981900 155450200 C -242246400 154562600 012962300 C -361769600 209663500 -036513600 H -441560600 238004500 031579700

S63

C -378506300 229550200 -173149400 H -470599200 272664600 -211305500 C -275036600 193991900 -260607700 H -286994900 209801900 -367568300 C -156335600 139000600 -211927100 H -078028800 113497900 -282765400 C -135806900 116871400 -074239700 N 149766100 056447500 -151960200 C 161044700 -045650000 -239517200 H 105570300 -135075200 -214908600 C 238601400 -038773000 -354326000 H 243317700 -124132500 -421011400 C 309437400 078767900 -379916800 H 372023600 087912200 -468136800 C 297881900 184648500 -290961800 H 350715200 277354700 -309620500 C 216303500 173511400 -177390900 C 191149200 280958700 -080874500 C 254076700 406532600 -087913900 H 327352800 427705400 -165284600 C 223210100 505175100 005238900 H 271947000 602111500 000140600 C 129017900 478269700 105132500 H 104205300 555047700 178071700 C 066955700 353199000 112146600 H -005039900 335649300 191665800 C 096122700 250789800 020375500 O 203118900 018918900 152088300 C 261106400 -088712700 191388100 O 338182000 -095412000 288161300 C 242934700 -218530400 110704500 H 263244700 -299133100 181200000 C 344465500 -228251600 -005437100 H 326901600 -145249300 -074321600 H 323044800 -320835500 -060630200 C 493189300 -227988600 035546100 H 513430800 -134362900 089079600 C 580496000 -230309300 -090752400 H 565052700 -322766900 -147850900 H 686869000 -224621400 -065129700 H 557497800 -146034900 -156946900 C 529504300 -343996600 129343800 H 502414500 -440892500 085398600 H 479269000 -334659000 226023400 H 637365700 -345592100 148676400 N 104772900 -246033700 063661000 C 063621600 -378634400 058011000 H 129144900 -459901300 085168700 C -064629500 -378317300 016052400 H -134408200 -458761400 -000900900 N -099973800 -245110600 -003511600 C 004831300 -160081900 025223200 C -236349300 -213847000 -040167500 C -332648500 -204776000 061944200 C -466153100 -184886300 024956900 H -541358600 -177192200 103102500 C -505461500 -176627800 -108967300 C -407390700 -191236600 -207662400 H -436391300 -188340100 -312417500 C -272522000 -210813500 -176026700 C -296522300 -221937700 207440000 H -272245600 -326536200 229894500 H -380262900 -193077000 271426500 H -209656600 -162185300 235809400 C -649516600 -151674600 -146256900 H -717390700 -180485900 -065450000 H -677861200 -206967000 -236380700 H -666470700 -045255700 -167014000 C -171412000 -229741900 -286305800 H -109733600 -140280500 -299308300 H -221819000 -249123900 -381355600 H -104063600 -313585400 -265935800

S2

Table of Contents 1 General Experimental procedures 3

2 Synthesis of Iridium-NHC complexes 4

21 Preparation of the imidazolium salts 4

22 Preparation of the silver-NHC complexes (S)-2 and (R)-2 5

23 Preparation of racemic [Ir(micro-Cl)(ppy)2]2 (1) 5

24 Preparation of the Iridium-NHC complexes 3 and 4 6

25 HPLC analyses for the Iridium-NHC complexes 3 and 4 8

26 Thermal and photochemical stability of D-(S)-4 9

3 Kinetic resolution studies 9

31 Preparation of racemic Ir-acac-5 9

32 HPLC analyses for reference samples 10

33 Kinetic resolution using the silver complex (S)-2 11

34 Kinetic resolution using the silver complex (R)-2 13

4 (Chiro)optical properties 15

41 UV-vis absorption 15

42 Emission spectra 15

43 Circularly Polarized Luminescence (CPL) 16

44 Electronic Circular Dichroism (ECD) 16

45 Vibrational Circular Dichroism (VCD) 18

46 Electrochemistry 21

5 Visible-light induced Ir-catalyzed Intermolecular [2+2] cycloaddition 22

6 Friedel Craft alkylation 23

61 General procedure for the synthesis of the Weinreb Amide 23

62 General procedure for the synthesis of acylimidazoles 24

63 Chiral Lewis-acid catalyzed Friedel Craft alkylation 25

7 NMR spectra 27

8 X-ray crystallographic data 40

9 Computational details 57

S3
























respectively










S4



























S5



772 (t J = 15Hz 1H) 714 (s 2H) 515-510 (m 1H) 237 (s 3H) 217 (m

2H) 209 (s 3H) 209 (s 3H) 152-142 (m 1H) 103 (d J = 66 Hz 3H) 099


1359 1357 1326 1307 1288 1247 1246 648 424 266 231 215
















927-924 (m 4H) 794 (d J = 82 Hz 4H) 782-777 (m 4H) 756 (dd J = 79

Hz 11 Hz 4H) 685-679 (m 8H) 663-658 (m 4H) 588 (dd J = 79 Hz 11


1304 1291 1237 1225 1213 1186


[ ]23Da

Cl

N

2

NIr

N N

O OH Cl

N N

O OH Cl

(S)-S1Cl

(R)-S1Cl

n

O OAg

N N

(R)-2

N N

AgO On (S)-2

S6














IrN

N

N N

OO

L-(S)-3

OO

N N

NN

Ir

D-(S)-4Ir-Cl-1

IrN

NCl

2

S7


(ppm) 904 (d J = 59 Hz 1H) 872 (d J = 58 Hz 1H)

789 (d J = 83 Hz 1H) 775 (t J = 82 Hz 1H) 763 (t

J = 83 Hz 1H) 751 (d J = 77 Hz 1H) 748 (d J = 82

Hz 1H) 726 (d J = 21 Hz 1H) 712 (d J = 67 Hz





(ppm) 1745 1733 1715 1681 1647 1525 1494 1453 1441 1425 1381 1366 1358 1346

1344 1338 1311 1299 1296 1285 1282 1276 1239 1234 1226 1219 1216 1211 1199






(ppm) 898 (d J = 51 Hz 1H) 845 (d J = 58 Hz 1H)

787 (d J = 84 Hz 1H) 774 (t J = 82 Hz 1H) 764 (t


688 (d J = 77 Hz 1H) 677 (t J = 73 Hz 1H) 666 (t





1493 1456 1441 1427 1383 1366 1358 1351 1344 1341 1309 1299 1292 1290 1282





[ ]23Da [ ]23Da

[ ]23Da [ ]23Da

IrN

N

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(R)-3

IrN

N

N N

OO

Λ-(S)-3

S8




1 L-(S)-3 14934 1651213 2080 28167

2 D-(R)-3 19353 1481456 1866 22306

3 L-(R)-4 28808 2311984 2913 14160

4 D-(S)-4 43480 2493060 3141 13653






14934

19353

28808

43480

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

15954

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

20203

AU

000

005

010

015

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

OO

N N

NN

Ir

Δ-(R)-3

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3Ir

NN

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(R)-3

S9




1 D-(S)-4 45556 4973589 10000 24208






modification








18471682 1482 1474 1451 1372 1332 1287 1238 1218 1208

1186 1003 283


29383

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

45556

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

N

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

ONN

Ir

O

S10






1 L-Cl-1 8459 100437 5013 5812

2 D-Cl-1 11259 99906 4987 4298



1 L-acac-5 8455 545111 5033 31569

2 D-acac-5 11257 538060 4967 23275



1 L-acac-5 8499 600487 813 34613

2 D-acac-5 11320 578535 784 24897

3 L-(S)-3 15085 1303525 1766 21522

4 D-(R)-3 19524 1177706 1595 17415

5 L-(R)-4 29368 1791550 2427 11078

6 D-(S)-4 44065 1929780 2614 10703


8459

11259

AU

0000

0002

0004

0006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8455

11257

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8499

11320

15085

19524

29368

44065AU

000

002

004

006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

rac-Ir-Cl-1

IrN

NCl

2

ONN

Ir

O

rac-Ir-acac-5

S11












DCE

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr


N N

AgO O2

Δ-(acac)-5 973 er

ONN

Ir

O

CH2Cl2 rtAg(acac)

Cl

N

2

Δ-(Cl)-1 973 er

NIr(S)-2


N

Ir

N

Cl2

IrN

N

N N

OO

Λ-(S)-3

Cl

N

2

Δ-(Cl)-1

NIr

S12

DCE







1 L-Cl-1 8438 13097 073 755

2 D-Cl-1 11216 567962 3171 24206

3 L-S-3 15012 1209965 6756 20418

4 D-S-3 - - - -


8438

11216

15012

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

Δ-(acac)-5

ONN

Ir

O

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr

Cl

N

2

Δ-(Cl)-1 973 er

NIr

S13


1 L-acac-5 8440 76761 142 4935

2 D-acac-5 11201 2544314 4708 109692

3 L-S-3 14563 2783501 5150 46214

4 D-S-3 - - - -












yield)

8440

11201

14563AU

000

005

010

015

020

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NOO

IrN

NCl

+

Δ-(R)-3 gt991 dr


N N

AgO O2

Λ-(acac)-5 973 er

CH2Cl2 rtAg(acac)

2

Λ-(Cl)-1 973 er

(R)-2O

O

N N

NN

Ir


N

Ir

N

Cl2

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr Δ-(acac)-5 973 er

ONN

Ir

O

S14





1 L-(Cl)-1 8438 547978 3816 31474

2 D-(Cl)-1 11241 19171 133 826

3 D-(R)-3 19550 868991 6051 12742

4 L-(R)-3 - - - -



1 L-(acac)-5 8416 2085477 4106 118534

2 D-(acac)-5 11223 73549 145 3560

3 D-(R)-3 18901 2919531 5749 41707

4 L-(R)-4 - - - -


8438

11241 19550AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8416

11223

18901

AU

000

002

004

006

008

010

012

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NCl

+

Δ-(R)-3 gt991 dr

2

Λ-(Cl)-1 973 er

OO

N N

NN

Ir

IrN

NOO

Λ-(acac)-5 973 er Δ-(R)-3 gt991 dr

OO

N N

NN

Ir+

S15




at 298 K (~10-5 M)

42 Emission spectra






nm-1)

Emission lmax nm


eV lmax nm t ns

D-(S)-4 267 (25700) 402 (2900) 478 (520)

508 520 (shoulder) 001a 851 487 522 558

(shoulder) 4400 255

L-(S)-3 267 (26100) 404 (3070) 480 (800)

508 518(shoulder) 001a 1048 487 522 558


S16






M)

S17



model




-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1


[ ]23Da

[ ]23Da

S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S3
























respectively










S4



























S5



772 (t J = 15Hz 1H) 714 (s 2H) 515-510 (m 1H) 237 (s 3H) 217 (m

2H) 209 (s 3H) 209 (s 3H) 152-142 (m 1H) 103 (d J = 66 Hz 3H) 099


1359 1357 1326 1307 1288 1247 1246 648 424 266 231 215
















927-924 (m 4H) 794 (d J = 82 Hz 4H) 782-777 (m 4H) 756 (dd J = 79

Hz 11 Hz 4H) 685-679 (m 8H) 663-658 (m 4H) 588 (dd J = 79 Hz 11


1304 1291 1237 1225 1213 1186


[ ]23Da

Cl

N

2

NIr

N N

O OH Cl

N N

O OH Cl

(S)-S1Cl

(R)-S1Cl

n

O OAg

N N

(R)-2

N N

AgO On (S)-2

S6














IrN

N

N N

OO

L-(S)-3

OO

N N

NN

Ir

D-(S)-4Ir-Cl-1

IrN

NCl

2

S7


(ppm) 904 (d J = 59 Hz 1H) 872 (d J = 58 Hz 1H)

789 (d J = 83 Hz 1H) 775 (t J = 82 Hz 1H) 763 (t

J = 83 Hz 1H) 751 (d J = 77 Hz 1H) 748 (d J = 82

Hz 1H) 726 (d J = 21 Hz 1H) 712 (d J = 67 Hz





(ppm) 1745 1733 1715 1681 1647 1525 1494 1453 1441 1425 1381 1366 1358 1346

1344 1338 1311 1299 1296 1285 1282 1276 1239 1234 1226 1219 1216 1211 1199






(ppm) 898 (d J = 51 Hz 1H) 845 (d J = 58 Hz 1H)

787 (d J = 84 Hz 1H) 774 (t J = 82 Hz 1H) 764 (t


688 (d J = 77 Hz 1H) 677 (t J = 73 Hz 1H) 666 (t





1493 1456 1441 1427 1383 1366 1358 1351 1344 1341 1309 1299 1292 1290 1282





[ ]23Da [ ]23Da

[ ]23Da [ ]23Da

IrN

N

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(R)-3

IrN

N

N N

OO

Λ-(S)-3

S8




1 L-(S)-3 14934 1651213 2080 28167

2 D-(R)-3 19353 1481456 1866 22306

3 L-(R)-4 28808 2311984 2913 14160

4 D-(S)-4 43480 2493060 3141 13653






14934

19353

28808

43480

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

15954

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

20203

AU

000

005

010

015

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

OO

N N

NN

Ir

Δ-(R)-3

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3Ir

NN

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(R)-3

S9




1 D-(S)-4 45556 4973589 10000 24208






modification








18471682 1482 1474 1451 1372 1332 1287 1238 1218 1208

1186 1003 283


29383

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

45556

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

N

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

ONN

Ir

O

S10






1 L-Cl-1 8459 100437 5013 5812

2 D-Cl-1 11259 99906 4987 4298



1 L-acac-5 8455 545111 5033 31569

2 D-acac-5 11257 538060 4967 23275



1 L-acac-5 8499 600487 813 34613

2 D-acac-5 11320 578535 784 24897

3 L-(S)-3 15085 1303525 1766 21522

4 D-(R)-3 19524 1177706 1595 17415

5 L-(R)-4 29368 1791550 2427 11078

6 D-(S)-4 44065 1929780 2614 10703


8459

11259

AU

0000

0002

0004

0006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8455

11257

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8499

11320

15085

19524

29368

44065AU

000

002

004

006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

rac-Ir-Cl-1

IrN

NCl

2

ONN

Ir

O

rac-Ir-acac-5

S11












DCE

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr


N N

AgO O2

Δ-(acac)-5 973 er

ONN

Ir

O

CH2Cl2 rtAg(acac)

Cl

N

2

Δ-(Cl)-1 973 er

NIr(S)-2


N

Ir

N

Cl2

IrN

N

N N

OO

Λ-(S)-3

Cl

N

2

Δ-(Cl)-1

NIr

S12

DCE







1 L-Cl-1 8438 13097 073 755

2 D-Cl-1 11216 567962 3171 24206

3 L-S-3 15012 1209965 6756 20418

4 D-S-3 - - - -


8438

11216

15012

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

Δ-(acac)-5

ONN

Ir

O

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr

Cl

N

2

Δ-(Cl)-1 973 er

NIr

S13


1 L-acac-5 8440 76761 142 4935

2 D-acac-5 11201 2544314 4708 109692

3 L-S-3 14563 2783501 5150 46214

4 D-S-3 - - - -












yield)

8440

11201

14563AU

000

005

010

015

020

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NOO

IrN

NCl

+

Δ-(R)-3 gt991 dr


N N

AgO O2

Λ-(acac)-5 973 er

CH2Cl2 rtAg(acac)

2

Λ-(Cl)-1 973 er

(R)-2O

O

N N

NN

Ir


N

Ir

N

Cl2

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr Δ-(acac)-5 973 er

ONN

Ir

O

S14





1 L-(Cl)-1 8438 547978 3816 31474

2 D-(Cl)-1 11241 19171 133 826

3 D-(R)-3 19550 868991 6051 12742

4 L-(R)-3 - - - -



1 L-(acac)-5 8416 2085477 4106 118534

2 D-(acac)-5 11223 73549 145 3560

3 D-(R)-3 18901 2919531 5749 41707

4 L-(R)-4 - - - -


8438

11241 19550AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8416

11223

18901

AU

000

002

004

006

008

010

012

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NCl

+

Δ-(R)-3 gt991 dr

2

Λ-(Cl)-1 973 er

OO

N N

NN

Ir

IrN

NOO

Λ-(acac)-5 973 er Δ-(R)-3 gt991 dr

OO

N N

NN

Ir+

S15




at 298 K (~10-5 M)

42 Emission spectra






nm-1)

Emission lmax nm


eV lmax nm t ns

D-(S)-4 267 (25700) 402 (2900) 478 (520)

508 520 (shoulder) 001a 851 487 522 558

(shoulder) 4400 255

L-(S)-3 267 (26100) 404 (3070) 480 (800)

508 518(shoulder) 001a 1048 487 522 558


S16






M)

S17



model




-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1


[ ]23Da

[ ]23Da

S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S4



























S5



772 (t J = 15Hz 1H) 714 (s 2H) 515-510 (m 1H) 237 (s 3H) 217 (m

2H) 209 (s 3H) 209 (s 3H) 152-142 (m 1H) 103 (d J = 66 Hz 3H) 099


1359 1357 1326 1307 1288 1247 1246 648 424 266 231 215
















927-924 (m 4H) 794 (d J = 82 Hz 4H) 782-777 (m 4H) 756 (dd J = 79

Hz 11 Hz 4H) 685-679 (m 8H) 663-658 (m 4H) 588 (dd J = 79 Hz 11


1304 1291 1237 1225 1213 1186


[ ]23Da

Cl

N

2

NIr

N N

O OH Cl

N N

O OH Cl

(S)-S1Cl

(R)-S1Cl

n

O OAg

N N

(R)-2

N N

AgO On (S)-2

S6














IrN

N

N N

OO

L-(S)-3

OO

N N

NN

Ir

D-(S)-4Ir-Cl-1

IrN

NCl

2

S7


(ppm) 904 (d J = 59 Hz 1H) 872 (d J = 58 Hz 1H)

789 (d J = 83 Hz 1H) 775 (t J = 82 Hz 1H) 763 (t

J = 83 Hz 1H) 751 (d J = 77 Hz 1H) 748 (d J = 82

Hz 1H) 726 (d J = 21 Hz 1H) 712 (d J = 67 Hz





(ppm) 1745 1733 1715 1681 1647 1525 1494 1453 1441 1425 1381 1366 1358 1346

1344 1338 1311 1299 1296 1285 1282 1276 1239 1234 1226 1219 1216 1211 1199






(ppm) 898 (d J = 51 Hz 1H) 845 (d J = 58 Hz 1H)

787 (d J = 84 Hz 1H) 774 (t J = 82 Hz 1H) 764 (t


688 (d J = 77 Hz 1H) 677 (t J = 73 Hz 1H) 666 (t





1493 1456 1441 1427 1383 1366 1358 1351 1344 1341 1309 1299 1292 1290 1282





[ ]23Da [ ]23Da

[ ]23Da [ ]23Da

IrN

N

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(R)-3

IrN

N

N N

OO

Λ-(S)-3

S8




1 L-(S)-3 14934 1651213 2080 28167

2 D-(R)-3 19353 1481456 1866 22306

3 L-(R)-4 28808 2311984 2913 14160

4 D-(S)-4 43480 2493060 3141 13653






14934

19353

28808

43480

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

15954

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

20203

AU

000

005

010

015

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

OO

N N

NN

Ir

Δ-(R)-3

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3Ir

NN

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(R)-3

S9




1 D-(S)-4 45556 4973589 10000 24208






modification








18471682 1482 1474 1451 1372 1332 1287 1238 1218 1208

1186 1003 283


29383

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

45556

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

N

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

ONN

Ir

O

S10






1 L-Cl-1 8459 100437 5013 5812

2 D-Cl-1 11259 99906 4987 4298



1 L-acac-5 8455 545111 5033 31569

2 D-acac-5 11257 538060 4967 23275



1 L-acac-5 8499 600487 813 34613

2 D-acac-5 11320 578535 784 24897

3 L-(S)-3 15085 1303525 1766 21522

4 D-(R)-3 19524 1177706 1595 17415

5 L-(R)-4 29368 1791550 2427 11078

6 D-(S)-4 44065 1929780 2614 10703


8459

11259

AU

0000

0002

0004

0006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8455

11257

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8499

11320

15085

19524

29368

44065AU

000

002

004

006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

rac-Ir-Cl-1

IrN

NCl

2

ONN

Ir

O

rac-Ir-acac-5

S11












DCE

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr


N N

AgO O2

Δ-(acac)-5 973 er

ONN

Ir

O

CH2Cl2 rtAg(acac)

Cl

N

2

Δ-(Cl)-1 973 er

NIr(S)-2


N

Ir

N

Cl2

IrN

N

N N

OO

Λ-(S)-3

Cl

N

2

Δ-(Cl)-1

NIr

S12

DCE







1 L-Cl-1 8438 13097 073 755

2 D-Cl-1 11216 567962 3171 24206

3 L-S-3 15012 1209965 6756 20418

4 D-S-3 - - - -


8438

11216

15012

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

Δ-(acac)-5

ONN

Ir

O

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr

Cl

N

2

Δ-(Cl)-1 973 er

NIr

S13


1 L-acac-5 8440 76761 142 4935

2 D-acac-5 11201 2544314 4708 109692

3 L-S-3 14563 2783501 5150 46214

4 D-S-3 - - - -












yield)

8440

11201

14563AU

000

005

010

015

020

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NOO

IrN

NCl

+

Δ-(R)-3 gt991 dr


N N

AgO O2

Λ-(acac)-5 973 er

CH2Cl2 rtAg(acac)

2

Λ-(Cl)-1 973 er

(R)-2O

O

N N

NN

Ir


N

Ir

N

Cl2

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr Δ-(acac)-5 973 er

ONN

Ir

O

S14





1 L-(Cl)-1 8438 547978 3816 31474

2 D-(Cl)-1 11241 19171 133 826

3 D-(R)-3 19550 868991 6051 12742

4 L-(R)-3 - - - -



1 L-(acac)-5 8416 2085477 4106 118534

2 D-(acac)-5 11223 73549 145 3560

3 D-(R)-3 18901 2919531 5749 41707

4 L-(R)-4 - - - -


8438

11241 19550AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8416

11223

18901

AU

000

002

004

006

008

010

012

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NCl

+

Δ-(R)-3 gt991 dr

2

Λ-(Cl)-1 973 er

OO

N N

NN

Ir

IrN

NOO

Λ-(acac)-5 973 er Δ-(R)-3 gt991 dr

OO

N N

NN

Ir+

S15




at 298 K (~10-5 M)

42 Emission spectra






nm-1)

Emission lmax nm


eV lmax nm t ns

D-(S)-4 267 (25700) 402 (2900) 478 (520)

508 520 (shoulder) 001a 851 487 522 558

(shoulder) 4400 255

L-(S)-3 267 (26100) 404 (3070) 480 (800)

508 518(shoulder) 001a 1048 487 522 558


S16






M)

S17



model




-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1


[ ]23Da

[ ]23Da

S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S5



772 (t J = 15Hz 1H) 714 (s 2H) 515-510 (m 1H) 237 (s 3H) 217 (m

2H) 209 (s 3H) 209 (s 3H) 152-142 (m 1H) 103 (d J = 66 Hz 3H) 099


1359 1357 1326 1307 1288 1247 1246 648 424 266 231 215
















927-924 (m 4H) 794 (d J = 82 Hz 4H) 782-777 (m 4H) 756 (dd J = 79

Hz 11 Hz 4H) 685-679 (m 8H) 663-658 (m 4H) 588 (dd J = 79 Hz 11


1304 1291 1237 1225 1213 1186


[ ]23Da

Cl

N

2

NIr

N N

O OH Cl

N N

O OH Cl

(S)-S1Cl

(R)-S1Cl

n

O OAg

N N

(R)-2

N N

AgO On (S)-2

S6














IrN

N

N N

OO

L-(S)-3

OO

N N

NN

Ir

D-(S)-4Ir-Cl-1

IrN

NCl

2

S7


(ppm) 904 (d J = 59 Hz 1H) 872 (d J = 58 Hz 1H)

789 (d J = 83 Hz 1H) 775 (t J = 82 Hz 1H) 763 (t

J = 83 Hz 1H) 751 (d J = 77 Hz 1H) 748 (d J = 82

Hz 1H) 726 (d J = 21 Hz 1H) 712 (d J = 67 Hz





(ppm) 1745 1733 1715 1681 1647 1525 1494 1453 1441 1425 1381 1366 1358 1346

1344 1338 1311 1299 1296 1285 1282 1276 1239 1234 1226 1219 1216 1211 1199






(ppm) 898 (d J = 51 Hz 1H) 845 (d J = 58 Hz 1H)

787 (d J = 84 Hz 1H) 774 (t J = 82 Hz 1H) 764 (t


688 (d J = 77 Hz 1H) 677 (t J = 73 Hz 1H) 666 (t





1493 1456 1441 1427 1383 1366 1358 1351 1344 1341 1309 1299 1292 1290 1282





[ ]23Da [ ]23Da

[ ]23Da [ ]23Da

IrN

N

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(R)-3

IrN

N

N N

OO

Λ-(S)-3

S8




1 L-(S)-3 14934 1651213 2080 28167

2 D-(R)-3 19353 1481456 1866 22306

3 L-(R)-4 28808 2311984 2913 14160

4 D-(S)-4 43480 2493060 3141 13653






14934

19353

28808

43480

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

15954

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

20203

AU

000

005

010

015

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

OO

N N

NN

Ir

Δ-(R)-3

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3Ir

NN

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(R)-3

S9




1 D-(S)-4 45556 4973589 10000 24208






modification








18471682 1482 1474 1451 1372 1332 1287 1238 1218 1208

1186 1003 283


29383

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

45556

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

N

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

ONN

Ir

O

S10






1 L-Cl-1 8459 100437 5013 5812

2 D-Cl-1 11259 99906 4987 4298



1 L-acac-5 8455 545111 5033 31569

2 D-acac-5 11257 538060 4967 23275



1 L-acac-5 8499 600487 813 34613

2 D-acac-5 11320 578535 784 24897

3 L-(S)-3 15085 1303525 1766 21522

4 D-(R)-3 19524 1177706 1595 17415

5 L-(R)-4 29368 1791550 2427 11078

6 D-(S)-4 44065 1929780 2614 10703


8459

11259

AU

0000

0002

0004

0006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8455

11257

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8499

11320

15085

19524

29368

44065AU

000

002

004

006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

rac-Ir-Cl-1

IrN

NCl

2

ONN

Ir

O

rac-Ir-acac-5

S11












DCE

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr


N N

AgO O2

Δ-(acac)-5 973 er

ONN

Ir

O

CH2Cl2 rtAg(acac)

Cl

N

2

Δ-(Cl)-1 973 er

NIr(S)-2


N

Ir

N

Cl2

IrN

N

N N

OO

Λ-(S)-3

Cl

N

2

Δ-(Cl)-1

NIr

S12

DCE







1 L-Cl-1 8438 13097 073 755

2 D-Cl-1 11216 567962 3171 24206

3 L-S-3 15012 1209965 6756 20418

4 D-S-3 - - - -


8438

11216

15012

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

Δ-(acac)-5

ONN

Ir

O

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr

Cl

N

2

Δ-(Cl)-1 973 er

NIr

S13


1 L-acac-5 8440 76761 142 4935

2 D-acac-5 11201 2544314 4708 109692

3 L-S-3 14563 2783501 5150 46214

4 D-S-3 - - - -












yield)

8440

11201

14563AU

000

005

010

015

020

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NOO

IrN

NCl

+

Δ-(R)-3 gt991 dr


N N

AgO O2

Λ-(acac)-5 973 er

CH2Cl2 rtAg(acac)

2

Λ-(Cl)-1 973 er

(R)-2O

O

N N

NN

Ir


N

Ir

N

Cl2

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr Δ-(acac)-5 973 er

ONN

Ir

O

S14





1 L-(Cl)-1 8438 547978 3816 31474

2 D-(Cl)-1 11241 19171 133 826

3 D-(R)-3 19550 868991 6051 12742

4 L-(R)-3 - - - -



1 L-(acac)-5 8416 2085477 4106 118534

2 D-(acac)-5 11223 73549 145 3560

3 D-(R)-3 18901 2919531 5749 41707

4 L-(R)-4 - - - -


8438

11241 19550AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8416

11223

18901

AU

000

002

004

006

008

010

012

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NCl

+

Δ-(R)-3 gt991 dr

2

Λ-(Cl)-1 973 er

OO

N N

NN

Ir

IrN

NOO

Λ-(acac)-5 973 er Δ-(R)-3 gt991 dr

OO

N N

NN

Ir+

S15




at 298 K (~10-5 M)

42 Emission spectra






nm-1)

Emission lmax nm


eV lmax nm t ns

D-(S)-4 267 (25700) 402 (2900) 478 (520)

508 520 (shoulder) 001a 851 487 522 558

(shoulder) 4400 255

L-(S)-3 267 (26100) 404 (3070) 480 (800)

508 518(shoulder) 001a 1048 487 522 558


S16






M)

S17



model




-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1


[ ]23Da

[ ]23Da

S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S6














IrN

N

N N

OO

L-(S)-3

OO

N N

NN

Ir

D-(S)-4Ir-Cl-1

IrN

NCl

2

S7


(ppm) 904 (d J = 59 Hz 1H) 872 (d J = 58 Hz 1H)

789 (d J = 83 Hz 1H) 775 (t J = 82 Hz 1H) 763 (t

J = 83 Hz 1H) 751 (d J = 77 Hz 1H) 748 (d J = 82

Hz 1H) 726 (d J = 21 Hz 1H) 712 (d J = 67 Hz





(ppm) 1745 1733 1715 1681 1647 1525 1494 1453 1441 1425 1381 1366 1358 1346

1344 1338 1311 1299 1296 1285 1282 1276 1239 1234 1226 1219 1216 1211 1199






(ppm) 898 (d J = 51 Hz 1H) 845 (d J = 58 Hz 1H)

787 (d J = 84 Hz 1H) 774 (t J = 82 Hz 1H) 764 (t


688 (d J = 77 Hz 1H) 677 (t J = 73 Hz 1H) 666 (t





1493 1456 1441 1427 1383 1366 1358 1351 1344 1341 1309 1299 1292 1290 1282





[ ]23Da [ ]23Da

[ ]23Da [ ]23Da

IrN

N

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(R)-3

IrN

N

N N

OO

Λ-(S)-3

S8




1 L-(S)-3 14934 1651213 2080 28167

2 D-(R)-3 19353 1481456 1866 22306

3 L-(R)-4 28808 2311984 2913 14160

4 D-(S)-4 43480 2493060 3141 13653






14934

19353

28808

43480

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

15954

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

20203

AU

000

005

010

015

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

OO

N N

NN

Ir

Δ-(R)-3

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3Ir

NN

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(R)-3

S9




1 D-(S)-4 45556 4973589 10000 24208






modification








18471682 1482 1474 1451 1372 1332 1287 1238 1218 1208

1186 1003 283


29383

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

45556

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

N

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

ONN

Ir

O

S10






1 L-Cl-1 8459 100437 5013 5812

2 D-Cl-1 11259 99906 4987 4298



1 L-acac-5 8455 545111 5033 31569

2 D-acac-5 11257 538060 4967 23275



1 L-acac-5 8499 600487 813 34613

2 D-acac-5 11320 578535 784 24897

3 L-(S)-3 15085 1303525 1766 21522

4 D-(R)-3 19524 1177706 1595 17415

5 L-(R)-4 29368 1791550 2427 11078

6 D-(S)-4 44065 1929780 2614 10703


8459

11259

AU

0000

0002

0004

0006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8455

11257

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8499

11320

15085

19524

29368

44065AU

000

002

004

006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

rac-Ir-Cl-1

IrN

NCl

2

ONN

Ir

O

rac-Ir-acac-5

S11












DCE

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr


N N

AgO O2

Δ-(acac)-5 973 er

ONN

Ir

O

CH2Cl2 rtAg(acac)

Cl

N

2

Δ-(Cl)-1 973 er

NIr(S)-2


N

Ir

N

Cl2

IrN

N

N N

OO

Λ-(S)-3

Cl

N

2

Δ-(Cl)-1

NIr

S12

DCE







1 L-Cl-1 8438 13097 073 755

2 D-Cl-1 11216 567962 3171 24206

3 L-S-3 15012 1209965 6756 20418

4 D-S-3 - - - -


8438

11216

15012

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

Δ-(acac)-5

ONN

Ir

O

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr

Cl

N

2

Δ-(Cl)-1 973 er

NIr

S13


1 L-acac-5 8440 76761 142 4935

2 D-acac-5 11201 2544314 4708 109692

3 L-S-3 14563 2783501 5150 46214

4 D-S-3 - - - -












yield)

8440

11201

14563AU

000

005

010

015

020

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NOO

IrN

NCl

+

Δ-(R)-3 gt991 dr


N N

AgO O2

Λ-(acac)-5 973 er

CH2Cl2 rtAg(acac)

2

Λ-(Cl)-1 973 er

(R)-2O

O

N N

NN

Ir


N

Ir

N

Cl2

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr Δ-(acac)-5 973 er

ONN

Ir

O

S14





1 L-(Cl)-1 8438 547978 3816 31474

2 D-(Cl)-1 11241 19171 133 826

3 D-(R)-3 19550 868991 6051 12742

4 L-(R)-3 - - - -



1 L-(acac)-5 8416 2085477 4106 118534

2 D-(acac)-5 11223 73549 145 3560

3 D-(R)-3 18901 2919531 5749 41707

4 L-(R)-4 - - - -


8438

11241 19550AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8416

11223

18901

AU

000

002

004

006

008

010

012

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NCl

+

Δ-(R)-3 gt991 dr

2

Λ-(Cl)-1 973 er

OO

N N

NN

Ir

IrN

NOO

Λ-(acac)-5 973 er Δ-(R)-3 gt991 dr

OO

N N

NN

Ir+

S15




at 298 K (~10-5 M)

42 Emission spectra






nm-1)

Emission lmax nm


eV lmax nm t ns

D-(S)-4 267 (25700) 402 (2900) 478 (520)

508 520 (shoulder) 001a 851 487 522 558

(shoulder) 4400 255

L-(S)-3 267 (26100) 404 (3070) 480 (800)

508 518(shoulder) 001a 1048 487 522 558


S16






M)

S17



model




-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1


[ ]23Da

[ ]23Da

S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S7


(ppm) 904 (d J = 59 Hz 1H) 872 (d J = 58 Hz 1H)

789 (d J = 83 Hz 1H) 775 (t J = 82 Hz 1H) 763 (t

J = 83 Hz 1H) 751 (d J = 77 Hz 1H) 748 (d J = 82

Hz 1H) 726 (d J = 21 Hz 1H) 712 (d J = 67 Hz





(ppm) 1745 1733 1715 1681 1647 1525 1494 1453 1441 1425 1381 1366 1358 1346

1344 1338 1311 1299 1296 1285 1282 1276 1239 1234 1226 1219 1216 1211 1199






(ppm) 898 (d J = 51 Hz 1H) 845 (d J = 58 Hz 1H)

787 (d J = 84 Hz 1H) 774 (t J = 82 Hz 1H) 764 (t


688 (d J = 77 Hz 1H) 677 (t J = 73 Hz 1H) 666 (t





1493 1456 1441 1427 1383 1366 1358 1351 1344 1341 1309 1299 1292 1290 1282





[ ]23Da [ ]23Da

[ ]23Da [ ]23Da

IrN

N

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(R)-3

IrN

N

N N

OO

Λ-(S)-3

S8




1 L-(S)-3 14934 1651213 2080 28167

2 D-(R)-3 19353 1481456 1866 22306

3 L-(R)-4 28808 2311984 2913 14160

4 D-(S)-4 43480 2493060 3141 13653






14934

19353

28808

43480

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

15954

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

20203

AU

000

005

010

015

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

OO

N N

NN

Ir

Δ-(R)-3

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3Ir

NN

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(R)-3

S9




1 D-(S)-4 45556 4973589 10000 24208






modification








18471682 1482 1474 1451 1372 1332 1287 1238 1218 1208

1186 1003 283


29383

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

45556

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

N

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

ONN

Ir

O

S10






1 L-Cl-1 8459 100437 5013 5812

2 D-Cl-1 11259 99906 4987 4298



1 L-acac-5 8455 545111 5033 31569

2 D-acac-5 11257 538060 4967 23275



1 L-acac-5 8499 600487 813 34613

2 D-acac-5 11320 578535 784 24897

3 L-(S)-3 15085 1303525 1766 21522

4 D-(R)-3 19524 1177706 1595 17415

5 L-(R)-4 29368 1791550 2427 11078

6 D-(S)-4 44065 1929780 2614 10703


8459

11259

AU

0000

0002

0004

0006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8455

11257

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8499

11320

15085

19524

29368

44065AU

000

002

004

006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

rac-Ir-Cl-1

IrN

NCl

2

ONN

Ir

O

rac-Ir-acac-5

S11












DCE

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr


N N

AgO O2

Δ-(acac)-5 973 er

ONN

Ir

O

CH2Cl2 rtAg(acac)

Cl

N

2

Δ-(Cl)-1 973 er

NIr(S)-2


N

Ir

N

Cl2

IrN

N

N N

OO

Λ-(S)-3

Cl

N

2

Δ-(Cl)-1

NIr

S12

DCE







1 L-Cl-1 8438 13097 073 755

2 D-Cl-1 11216 567962 3171 24206

3 L-S-3 15012 1209965 6756 20418

4 D-S-3 - - - -


8438

11216

15012

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

Δ-(acac)-5

ONN

Ir

O

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr

Cl

N

2

Δ-(Cl)-1 973 er

NIr

S13


1 L-acac-5 8440 76761 142 4935

2 D-acac-5 11201 2544314 4708 109692

3 L-S-3 14563 2783501 5150 46214

4 D-S-3 - - - -












yield)

8440

11201

14563AU

000

005

010

015

020

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NOO

IrN

NCl

+

Δ-(R)-3 gt991 dr


N N

AgO O2

Λ-(acac)-5 973 er

CH2Cl2 rtAg(acac)

2

Λ-(Cl)-1 973 er

(R)-2O

O

N N

NN

Ir


N

Ir

N

Cl2

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr Δ-(acac)-5 973 er

ONN

Ir

O

S14





1 L-(Cl)-1 8438 547978 3816 31474

2 D-(Cl)-1 11241 19171 133 826

3 D-(R)-3 19550 868991 6051 12742

4 L-(R)-3 - - - -



1 L-(acac)-5 8416 2085477 4106 118534

2 D-(acac)-5 11223 73549 145 3560

3 D-(R)-3 18901 2919531 5749 41707

4 L-(R)-4 - - - -


8438

11241 19550AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8416

11223

18901

AU

000

002

004

006

008

010

012

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NCl

+

Δ-(R)-3 gt991 dr

2

Λ-(Cl)-1 973 er

OO

N N

NN

Ir

IrN

NOO

Λ-(acac)-5 973 er Δ-(R)-3 gt991 dr

OO

N N

NN

Ir+

S15




at 298 K (~10-5 M)

42 Emission spectra






nm-1)

Emission lmax nm


eV lmax nm t ns

D-(S)-4 267 (25700) 402 (2900) 478 (520)

508 520 (shoulder) 001a 851 487 522 558

(shoulder) 4400 255

L-(S)-3 267 (26100) 404 (3070) 480 (800)

508 518(shoulder) 001a 1048 487 522 558


S16






M)

S17



model




-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1


[ ]23Da

[ ]23Da

S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S8




1 L-(S)-3 14934 1651213 2080 28167

2 D-(R)-3 19353 1481456 1866 22306

3 L-(R)-4 28808 2311984 2913 14160

4 D-(S)-4 43480 2493060 3141 13653






14934

19353

28808

43480

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

15954

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

20203

AU

000

005

010

015

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

OO

N N

NN

Ir

Δ-(R)-3

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3Ir

NN

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(R)-3

S9




1 D-(S)-4 45556 4973589 10000 24208






modification








18471682 1482 1474 1451 1372 1332 1287 1238 1218 1208

1186 1003 283


29383

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

45556

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

N

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

ONN

Ir

O

S10






1 L-Cl-1 8459 100437 5013 5812

2 D-Cl-1 11259 99906 4987 4298



1 L-acac-5 8455 545111 5033 31569

2 D-acac-5 11257 538060 4967 23275



1 L-acac-5 8499 600487 813 34613

2 D-acac-5 11320 578535 784 24897

3 L-(S)-3 15085 1303525 1766 21522

4 D-(R)-3 19524 1177706 1595 17415

5 L-(R)-4 29368 1791550 2427 11078

6 D-(S)-4 44065 1929780 2614 10703


8459

11259

AU

0000

0002

0004

0006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8455

11257

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8499

11320

15085

19524

29368

44065AU

000

002

004

006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

rac-Ir-Cl-1

IrN

NCl

2

ONN

Ir

O

rac-Ir-acac-5

S11












DCE

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr


N N

AgO O2

Δ-(acac)-5 973 er

ONN

Ir

O

CH2Cl2 rtAg(acac)

Cl

N

2

Δ-(Cl)-1 973 er

NIr(S)-2


N

Ir

N

Cl2

IrN

N

N N

OO

Λ-(S)-3

Cl

N

2

Δ-(Cl)-1

NIr

S12

DCE







1 L-Cl-1 8438 13097 073 755

2 D-Cl-1 11216 567962 3171 24206

3 L-S-3 15012 1209965 6756 20418

4 D-S-3 - - - -


8438

11216

15012

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

Δ-(acac)-5

ONN

Ir

O

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr

Cl

N

2

Δ-(Cl)-1 973 er

NIr

S13


1 L-acac-5 8440 76761 142 4935

2 D-acac-5 11201 2544314 4708 109692

3 L-S-3 14563 2783501 5150 46214

4 D-S-3 - - - -












yield)

8440

11201

14563AU

000

005

010

015

020

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NOO

IrN

NCl

+

Δ-(R)-3 gt991 dr


N N

AgO O2

Λ-(acac)-5 973 er

CH2Cl2 rtAg(acac)

2

Λ-(Cl)-1 973 er

(R)-2O

O

N N

NN

Ir


N

Ir

N

Cl2

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr Δ-(acac)-5 973 er

ONN

Ir

O

S14





1 L-(Cl)-1 8438 547978 3816 31474

2 D-(Cl)-1 11241 19171 133 826

3 D-(R)-3 19550 868991 6051 12742

4 L-(R)-3 - - - -



1 L-(acac)-5 8416 2085477 4106 118534

2 D-(acac)-5 11223 73549 145 3560

3 D-(R)-3 18901 2919531 5749 41707

4 L-(R)-4 - - - -


8438

11241 19550AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8416

11223

18901

AU

000

002

004

006

008

010

012

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NCl

+

Δ-(R)-3 gt991 dr

2

Λ-(Cl)-1 973 er

OO

N N

NN

Ir

IrN

NOO

Λ-(acac)-5 973 er Δ-(R)-3 gt991 dr

OO

N N

NN

Ir+

S15




at 298 K (~10-5 M)

42 Emission spectra






nm-1)

Emission lmax nm


eV lmax nm t ns

D-(S)-4 267 (25700) 402 (2900) 478 (520)

508 520 (shoulder) 001a 851 487 522 558

(shoulder) 4400 255

L-(S)-3 267 (26100) 404 (3070) 480 (800)

508 518(shoulder) 001a 1048 487 522 558


S16






M)

S17



model




-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1


[ ]23Da

[ ]23Da

S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S9




1 D-(S)-4 45556 4973589 10000 24208






modification








18471682 1482 1474 1451 1372 1332 1287 1238 1218 1208

1186 1003 283


29383

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500

45556

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

N

N N

OO

Λ-(R)-4

OO

N N

NN

Ir

Δ-(S)-4

ONN

Ir

O

S10






1 L-Cl-1 8459 100437 5013 5812

2 D-Cl-1 11259 99906 4987 4298



1 L-acac-5 8455 545111 5033 31569

2 D-acac-5 11257 538060 4967 23275



1 L-acac-5 8499 600487 813 34613

2 D-acac-5 11320 578535 784 24897

3 L-(S)-3 15085 1303525 1766 21522

4 D-(R)-3 19524 1177706 1595 17415

5 L-(R)-4 29368 1791550 2427 11078

6 D-(S)-4 44065 1929780 2614 10703


8459

11259

AU

0000

0002

0004

0006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8455

11257

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8499

11320

15085

19524

29368

44065AU

000

002

004

006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

rac-Ir-Cl-1

IrN

NCl

2

ONN

Ir

O

rac-Ir-acac-5

S11












DCE

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr


N N

AgO O2

Δ-(acac)-5 973 er

ONN

Ir

O

CH2Cl2 rtAg(acac)

Cl

N

2

Δ-(Cl)-1 973 er

NIr(S)-2


N

Ir

N

Cl2

IrN

N

N N

OO

Λ-(S)-3

Cl

N

2

Δ-(Cl)-1

NIr

S12

DCE







1 L-Cl-1 8438 13097 073 755

2 D-Cl-1 11216 567962 3171 24206

3 L-S-3 15012 1209965 6756 20418

4 D-S-3 - - - -


8438

11216

15012

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

Δ-(acac)-5

ONN

Ir

O

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr

Cl

N

2

Δ-(Cl)-1 973 er

NIr

S13


1 L-acac-5 8440 76761 142 4935

2 D-acac-5 11201 2544314 4708 109692

3 L-S-3 14563 2783501 5150 46214

4 D-S-3 - - - -












yield)

8440

11201

14563AU

000

005

010

015

020

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NOO

IrN

NCl

+

Δ-(R)-3 gt991 dr


N N

AgO O2

Λ-(acac)-5 973 er

CH2Cl2 rtAg(acac)

2

Λ-(Cl)-1 973 er

(R)-2O

O

N N

NN

Ir


N

Ir

N

Cl2

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr Δ-(acac)-5 973 er

ONN

Ir

O

S14





1 L-(Cl)-1 8438 547978 3816 31474

2 D-(Cl)-1 11241 19171 133 826

3 D-(R)-3 19550 868991 6051 12742

4 L-(R)-3 - - - -



1 L-(acac)-5 8416 2085477 4106 118534

2 D-(acac)-5 11223 73549 145 3560

3 D-(R)-3 18901 2919531 5749 41707

4 L-(R)-4 - - - -


8438

11241 19550AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8416

11223

18901

AU

000

002

004

006

008

010

012

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NCl

+

Δ-(R)-3 gt991 dr

2

Λ-(Cl)-1 973 er

OO

N N

NN

Ir

IrN

NOO

Λ-(acac)-5 973 er Δ-(R)-3 gt991 dr

OO

N N

NN

Ir+

S15




at 298 K (~10-5 M)

42 Emission spectra






nm-1)

Emission lmax nm


eV lmax nm t ns

D-(S)-4 267 (25700) 402 (2900) 478 (520)

508 520 (shoulder) 001a 851 487 522 558

(shoulder) 4400 255

L-(S)-3 267 (26100) 404 (3070) 480 (800)

508 518(shoulder) 001a 1048 487 522 558


S16






M)

S17



model




-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1


[ ]23Da

[ ]23Da

S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S10






1 L-Cl-1 8459 100437 5013 5812

2 D-Cl-1 11259 99906 4987 4298



1 L-acac-5 8455 545111 5033 31569

2 D-acac-5 11257 538060 4967 23275



1 L-acac-5 8499 600487 813 34613

2 D-acac-5 11320 578535 784 24897

3 L-(S)-3 15085 1303525 1766 21522

4 D-(R)-3 19524 1177706 1595 17415

5 L-(R)-4 29368 1791550 2427 11078

6 D-(S)-4 44065 1929780 2614 10703


8459

11259

AU

0000

0002

0004

0006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8455

11257

AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8499

11320

15085

19524

29368

44065AU

000

002

004

006

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

rac-Ir-Cl-1

IrN

NCl

2

ONN

Ir

O

rac-Ir-acac-5

S11












DCE

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr


N N

AgO O2

Δ-(acac)-5 973 er

ONN

Ir

O

CH2Cl2 rtAg(acac)

Cl

N

2

Δ-(Cl)-1 973 er

NIr(S)-2


N

Ir

N

Cl2

IrN

N

N N

OO

Λ-(S)-3

Cl

N

2

Δ-(Cl)-1

NIr

S12

DCE







1 L-Cl-1 8438 13097 073 755

2 D-Cl-1 11216 567962 3171 24206

3 L-S-3 15012 1209965 6756 20418

4 D-S-3 - - - -


8438

11216

15012

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

Δ-(acac)-5

ONN

Ir

O

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr

Cl

N

2

Δ-(Cl)-1 973 er

NIr

S13


1 L-acac-5 8440 76761 142 4935

2 D-acac-5 11201 2544314 4708 109692

3 L-S-3 14563 2783501 5150 46214

4 D-S-3 - - - -












yield)

8440

11201

14563AU

000

005

010

015

020

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NOO

IrN

NCl

+

Δ-(R)-3 gt991 dr


N N

AgO O2

Λ-(acac)-5 973 er

CH2Cl2 rtAg(acac)

2

Λ-(Cl)-1 973 er

(R)-2O

O

N N

NN

Ir


N

Ir

N

Cl2

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr Δ-(acac)-5 973 er

ONN

Ir

O

S14





1 L-(Cl)-1 8438 547978 3816 31474

2 D-(Cl)-1 11241 19171 133 826

3 D-(R)-3 19550 868991 6051 12742

4 L-(R)-3 - - - -



1 L-(acac)-5 8416 2085477 4106 118534

2 D-(acac)-5 11223 73549 145 3560

3 D-(R)-3 18901 2919531 5749 41707

4 L-(R)-4 - - - -


8438

11241 19550AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8416

11223

18901

AU

000

002

004

006

008

010

012

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NCl

+

Δ-(R)-3 gt991 dr

2

Λ-(Cl)-1 973 er

OO

N N

NN

Ir

IrN

NOO

Λ-(acac)-5 973 er Δ-(R)-3 gt991 dr

OO

N N

NN

Ir+

S15




at 298 K (~10-5 M)

42 Emission spectra






nm-1)

Emission lmax nm


eV lmax nm t ns

D-(S)-4 267 (25700) 402 (2900) 478 (520)

508 520 (shoulder) 001a 851 487 522 558

(shoulder) 4400 255

L-(S)-3 267 (26100) 404 (3070) 480 (800)

508 518(shoulder) 001a 1048 487 522 558


S16






M)

S17



model




-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1


[ ]23Da

[ ]23Da

S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S11












DCE

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr


N N

AgO O2

Δ-(acac)-5 973 er

ONN

Ir

O

CH2Cl2 rtAg(acac)

Cl

N

2

Δ-(Cl)-1 973 er

NIr(S)-2


N

Ir

N

Cl2

IrN

N

N N

OO

Λ-(S)-3

Cl

N

2

Δ-(Cl)-1

NIr

S12

DCE







1 L-Cl-1 8438 13097 073 755

2 D-Cl-1 11216 567962 3171 24206

3 L-S-3 15012 1209965 6756 20418

4 D-S-3 - - - -


8438

11216

15012

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

Δ-(acac)-5

ONN

Ir

O

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr

Cl

N

2

Δ-(Cl)-1 973 er

NIr

S13


1 L-acac-5 8440 76761 142 4935

2 D-acac-5 11201 2544314 4708 109692

3 L-S-3 14563 2783501 5150 46214

4 D-S-3 - - - -












yield)

8440

11201

14563AU

000

005

010

015

020

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NOO

IrN

NCl

+

Δ-(R)-3 gt991 dr


N N

AgO O2

Λ-(acac)-5 973 er

CH2Cl2 rtAg(acac)

2

Λ-(Cl)-1 973 er

(R)-2O

O

N N

NN

Ir


N

Ir

N

Cl2

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr Δ-(acac)-5 973 er

ONN

Ir

O

S14





1 L-(Cl)-1 8438 547978 3816 31474

2 D-(Cl)-1 11241 19171 133 826

3 D-(R)-3 19550 868991 6051 12742

4 L-(R)-3 - - - -



1 L-(acac)-5 8416 2085477 4106 118534

2 D-(acac)-5 11223 73549 145 3560

3 D-(R)-3 18901 2919531 5749 41707

4 L-(R)-4 - - - -


8438

11241 19550AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8416

11223

18901

AU

000

002

004

006

008

010

012

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NCl

+

Δ-(R)-3 gt991 dr

2

Λ-(Cl)-1 973 er

OO

N N

NN

Ir

IrN

NOO

Λ-(acac)-5 973 er Δ-(R)-3 gt991 dr

OO

N N

NN

Ir+

S15




at 298 K (~10-5 M)

42 Emission spectra






nm-1)

Emission lmax nm


eV lmax nm t ns

D-(S)-4 267 (25700) 402 (2900) 478 (520)

508 520 (shoulder) 001a 851 487 522 558

(shoulder) 4400 255

L-(S)-3 267 (26100) 404 (3070) 480 (800)

508 518(shoulder) 001a 1048 487 522 558


S16






M)

S17



model




-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1


[ ]23Da

[ ]23Da

S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S12

DCE







1 L-Cl-1 8438 13097 073 755

2 D-Cl-1 11216 567962 3171 24206

3 L-S-3 15012 1209965 6756 20418

4 D-S-3 - - - -


8438

11216

15012

AU

0000

0010

0020

0030

0040

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

Δ-(acac)-5

ONN

Ir

O

IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr

Cl

N

2

Δ-(Cl)-1 973 er

NIr

S13


1 L-acac-5 8440 76761 142 4935

2 D-acac-5 11201 2544314 4708 109692

3 L-S-3 14563 2783501 5150 46214

4 D-S-3 - - - -












yield)

8440

11201

14563AU

000

005

010

015

020

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NOO

IrN

NCl

+

Δ-(R)-3 gt991 dr


N N

AgO O2

Λ-(acac)-5 973 er

CH2Cl2 rtAg(acac)

2

Λ-(Cl)-1 973 er

(R)-2O

O

N N

NN

Ir


N

Ir

N

Cl2

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr Δ-(acac)-5 973 er

ONN

Ir

O

S14





1 L-(Cl)-1 8438 547978 3816 31474

2 D-(Cl)-1 11241 19171 133 826

3 D-(R)-3 19550 868991 6051 12742

4 L-(R)-3 - - - -



1 L-(acac)-5 8416 2085477 4106 118534

2 D-(acac)-5 11223 73549 145 3560

3 D-(R)-3 18901 2919531 5749 41707

4 L-(R)-4 - - - -


8438

11241 19550AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8416

11223

18901

AU

000

002

004

006

008

010

012

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NCl

+

Δ-(R)-3 gt991 dr

2

Λ-(Cl)-1 973 er

OO

N N

NN

Ir

IrN

NOO

Λ-(acac)-5 973 er Δ-(R)-3 gt991 dr

OO

N N

NN

Ir+

S15




at 298 K (~10-5 M)

42 Emission spectra






nm-1)

Emission lmax nm


eV lmax nm t ns

D-(S)-4 267 (25700) 402 (2900) 478 (520)

508 520 (shoulder) 001a 851 487 522 558

(shoulder) 4400 255

L-(S)-3 267 (26100) 404 (3070) 480 (800)

508 518(shoulder) 001a 1048 487 522 558


S16






M)

S17



model




-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1


[ ]23Da

[ ]23Da

S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S13


1 L-acac-5 8440 76761 142 4935

2 D-acac-5 11201 2544314 4708 109692

3 L-S-3 14563 2783501 5150 46214

4 D-S-3 - - - -












yield)

8440

11201

14563AU

000

005

010

015

020

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NOO

IrN

NCl

+

Δ-(R)-3 gt991 dr


N N

AgO O2

Λ-(acac)-5 973 er

CH2Cl2 rtAg(acac)

2

Λ-(Cl)-1 973 er

(R)-2O

O

N N

NN

Ir


N

Ir

N

Cl2

IrN

N

N N

OO

+

Λ-(S)-3 gt991 dr Δ-(acac)-5 973 er

ONN

Ir

O

S14





1 L-(Cl)-1 8438 547978 3816 31474

2 D-(Cl)-1 11241 19171 133 826

3 D-(R)-3 19550 868991 6051 12742

4 L-(R)-3 - - - -



1 L-(acac)-5 8416 2085477 4106 118534

2 D-(acac)-5 11223 73549 145 3560

3 D-(R)-3 18901 2919531 5749 41707

4 L-(R)-4 - - - -


8438

11241 19550AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8416

11223

18901

AU

000

002

004

006

008

010

012

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NCl

+

Δ-(R)-3 gt991 dr

2

Λ-(Cl)-1 973 er

OO

N N

NN

Ir

IrN

NOO

Λ-(acac)-5 973 er Δ-(R)-3 gt991 dr

OO

N N

NN

Ir+

S15




at 298 K (~10-5 M)

42 Emission spectra






nm-1)

Emission lmax nm


eV lmax nm t ns

D-(S)-4 267 (25700) 402 (2900) 478 (520)

508 520 (shoulder) 001a 851 487 522 558

(shoulder) 4400 255

L-(S)-3 267 (26100) 404 (3070) 480 (800)

508 518(shoulder) 001a 1048 487 522 558


S16






M)

S17



model




-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1


[ ]23Da

[ ]23Da

S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S14





1 L-(Cl)-1 8438 547978 3816 31474

2 D-(Cl)-1 11241 19171 133 826

3 D-(R)-3 19550 868991 6051 12742

4 L-(R)-3 - - - -



1 L-(acac)-5 8416 2085477 4106 118534

2 D-(acac)-5 11223 73549 145 3560

3 D-(R)-3 18901 2919531 5749 41707

4 L-(R)-4 - - - -


8438

11241 19550AU

0000

0010

0020

0030

0040

0050

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

8416

11223

18901

AU

000

002

004

006

008

010

012

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

IrN

NCl

+

Δ-(R)-3 gt991 dr

2

Λ-(Cl)-1 973 er

OO

N N

NN

Ir

IrN

NOO

Λ-(acac)-5 973 er Δ-(R)-3 gt991 dr

OO

N N

NN

Ir+

S15




at 298 K (~10-5 M)

42 Emission spectra






nm-1)

Emission lmax nm


eV lmax nm t ns

D-(S)-4 267 (25700) 402 (2900) 478 (520)

508 520 (shoulder) 001a 851 487 522 558

(shoulder) 4400 255

L-(S)-3 267 (26100) 404 (3070) 480 (800)

508 518(shoulder) 001a 1048 487 522 558


S16






M)

S17



model




-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1


[ ]23Da

[ ]23Da

S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S15




at 298 K (~10-5 M)

42 Emission spectra






nm-1)

Emission lmax nm


eV lmax nm t ns

D-(S)-4 267 (25700) 402 (2900) 478 (520)

508 520 (shoulder) 001a 851 487 522 558

(shoulder) 4400 255

L-(S)-3 267 (26100) 404 (3070) 480 (800)

508 518(shoulder) 001a 1048 487 522 558


S16






M)

S17



model




-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1


[ ]23Da

[ ]23Da

S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S16






M)

S17



model




-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1


[ ]23Da

[ ]23Da

S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S17



model




-40

-30

-20

-10

0

10

20

250 350 450 550l nm

De

M-1

cm

-1


[ ]23Da

[ ]23Da

S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S18







-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(LIr SC)-3

(DIr RC)-3

a)

b)

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

0

500

1000

1500

10001200140016001800

n cm-1

e

M-1

cm

-1

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

a)

b)

S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S19




-2000000000

-1500000000

-1000000000

-500000000

0000000

500000000

1000000000

1500000000

10001200140016001800n cm-1

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M-1

cm

-1

(DIr RC)-3

(LIr SC)-3

a)(LIr SC)-3

-150E-01-100E-01-500E-02000E+00500E-02100E-01150E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

b)

c)

(LIr SC)-3

S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S20




-1500

-1000

-500

0

500

1000

1500

2000

10001200140016001800n cm-1

-180E-01-130E-01-800E-02-300E-02200E-02700E-02120E-01170E-01

10001200140016001800

n cm-1

De

M

-1 c

m-1

a)(DIr SC)-4

b)

c)

-170E-01-120E-01-700E-02-200E-02300E-02800E-02130E-01

10001200140016001800

n cm-1

De

M-1

cm

-1 (DIr SC)-4

(LIr RC)-4

c)

(DIr SC)-4

S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S21

46 Electrochemistry






ERed Ir(III)Ir(II)

L-(S)-3 085 -210

D-(S)-4 084 -210

S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S22











1284 1287 1285 1280 1279 1271 1263 1261 7736 542 530 393 344





1 9 16498 2290102 5019 37159

2 9 21793 2273080 4981 31789



Λ-(S)-3 or Δ-(S)-4

Ph OH

O

Ph

Ph+

OHO

Ph

PhPh


(1 mol)

7 8

16498

21793

AU

0000

0010

0020

0030

Minutes1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000

OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S23













Hz 1H) 767-760 (m 6H) 748-743 (m 2H) 739-735 (m 1H)



[M+Na]+ 2901154 (1 ppm) mp 125-128degC




1H) 743-739 (m 1H) 734-728 (m 1H) 726-722 (m 1H) 702 (d J =




H

O

(EtO)2PN

OOO

MeMe

+ N

OO

MeMe


R R

S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S24












(m 4H) 747-742 (m 2H) 738-733 (m 1H) 723 (d J = 10 Hz 1H) 708







783 (d J = 160 Hz 1H) 757-750 (m 2H) 733-723 (m 4H) 708 (m 1H)


MHz CDCl3) δ (ppm) 1807 1496 1442 1440 1350 1294 1290 1289 1273 1268 1268

1225 365 342 241



N

OO

MeMe

O

N

N


-78degC - rt 12hR R

11

O

N

N

11a

O

N

N

11b

S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S25

















1 12a 25932 2617720 5056 37149

2 12a 31018 2559575 4944 36138


Δ-Cl-1 (973 er) (5 mol)

O

N

N

NH

THF rt 24h

O

N

N

NH

+

R R

11

10

AgPF6 (10 mol)

12a-b

25932

31018

AU

0000

0010

0020

0030

0040

0050

0060

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

O

N

N

NH12a

S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S26


1 12a 26579 503322 2142 6931

2 12a 31297 1846316 7858 25549







1283 1270 1264 1254 1241 1220 1216 1197 1193 1110 455




1 12b 10539 6968473 5078 282809

2 12b 17187 6753536 4922 173727


26579

31297

AU

0000

0010

0020

0030

0040

Minutes1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400 4600 4800 5000

10539

17187

AU

000

010

020

030

040

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

12b

O

N

N

NH

S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S27


1 12b 10622 775511 2444 30491

2 12b 17451 2398216 7556 59568


7 NMR spectra


10622 17451

AU

000

005

010

015

Minutes800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

OHO

N N

Cl

S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S28



n

O OAg

N N

(R)-2

N N

AgO On (S)-2

OHO

N N

Cl

S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S29



IrN

N

N N

OO

Λ-(S)-3

IrN

N

N N

OO

Λ-(S)-3

S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S30



OO

N N

NN

Ir

Δ-(S)-4

OO

N N

NN

Ir

Δ-(S)-4

S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S31



OO

N N

NN

Ir

Δ-(R)-3

OO

N N

NN

Ir

Δ-(R)-3

S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S32



IrN

N

N N

OO

Λ-(R)-4

IrN

N

N N

OO

Λ-(R)-4

S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S33



OHO

Ph

PhPh rac-9

OHO

Ph

PhPh rac-9

S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S34



N

OO

MeMe

N

OO

MeMe

S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S35



N

OO

MeMe

N

OO

MeMe

S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S36



O

N

N

11a

O

N

N

11a

S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S37



O

N

N

11b

O

N

N

11b

S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S38



O

N

N

NH12a

O

N

N

NH12a

S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S39



12b

O

N

N

NH

12b

O

N

N

NH

S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S40













S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S41




S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S42


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S43






S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S44


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S45


Angles [deg]


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S46


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S47




S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S48


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S49















S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S50



S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S51





S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S52

C45 0028(4) 0019(5) 0016(4) 0003(3) -0004(3) 0000(3) O101 0030(3) 0018(3) 0053(4) 0000(3) 0003(3) 0004(3)



S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S53


Angles [deg]


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S54


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S55



S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S56


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S57



















S58




Ir O

N

CO

S59



S60



S61



S62



S63


S58




Ir O

N

CO

S59



S60



S61



S62



S63


S59



S60



S61



S62



S63


S60



S61



S62



S63


S61



S62



S63


S62



S63


S63


si kr chemcomm 24:03:2019 - rsc.org · melting points were measured on a stuart® smp 10 melting...

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