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SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.1088

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[Submitted to Nature Chemistry]

Supplementary Information:

A Coordination Chemistry Dichotomy for Icosahedral Carborane-Based Ligands

Alexander M. Spokoyny, Charles W. Machan, Daniel J. Clingerman, Mari S. Rosen, Michael J.

Wiester, Robert D. Kennedy, Charlotte L. Stern, Amy A. Sarjeant, and Chad A. Mirkin*

1Department of Chemistry and the International Institute for Nanotechnology

Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, USA

*Corresponding Author:

Chad A. Mirkin

Email: [email protected]

Phone: (+1) 847-467-7302; Fax: (+1) 847-467-5123

© 2011 Macmillan Publishers Limited. All rights reserved.



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Table of Contents:

1. Synthetic procedures and characterization ……………………………………S3-S21 2. Additional NMR spectra ……………………………………………………...S22-S24 3. Crystallographic structure determination and refinement details ………….…S24-S51 4. Computational details……………………………………………………........S52-S75 5. References……………………………………………………………....………….S76




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1. Synthetic Procedures.

A. General considerations: 1,2-dicarba-closo-dodecaborane (o-carborane) and 1,7-dicarba-

closo-dodecaborane (m-carborane) were purchased from Katchem (Czech Republic, price per

gram if ordered on a scale > 100g is approximately 22$) and used as received. Selenium

monochloride (Se2Cl2) was purchased from Strem Chemicals and was used as received. All other

solvents and chemicals were obtained from Aldrich Chemical Co. (Milwaukee, USA).

Deuterated solvents were purchased from Cambridge Isotope Laboratories and used as received.

Carborane thiols were prepared according to procedures established by Plesek et al.1 and

Zakharkin et al.2 For I, II, III, and V full characterization is provided below (pp. 5-6). Carborane

selenols were prepared according to modified procedures established by Zakharkin et al.3-4

Syntheses of ligands 1g-1i,5 and their Pt(II) complexes 2h, 2i, 3h were reported previously.6

Large scale preparation of 1-Chloro-2-diphenylphosphinoethane was used according to a

previously reported procedure.7 P, S ligands 1a-1d were found to be stable towards oxidation of

the phosphine both when stored as solids and in solution under ambient conditions over normal

reaction periods (at least 3 weeks via 31P{1H} NMR). For Pt(II) complexes with carbon-based

ligands (1e-1i) NMR data was obtained in situ from reactions conducted in CD2Cl2. Unless

otherwise noted, all yields for Pt(II) complexes are 100%, as observed from 31P NMR. For all

air-sensitive manipulations outlined below either Vacuum Atmospheres Nexus N2-filled glove

box or proper Schlenk techniques were employed. Analytical thin layer chromatography (TLC)

was performed using glass plates pre-coated with silica gel (0.25 mm, 60 Å pore size) with a

fluorescent indicator (254 nm). Visualization was accomplished with UV light and/or palladium

chloride (PdCl2) in ca. 6 M hydrochloric acid as a stain. All NMR spectra were recorded Bruker

Avance 400MHz equipped with a broadband probe. 1H and 13C{1H} NMR were referenced to




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residual proton and carbon resonances in deuterated solvents. 11B/11B{1H} NMR was referenced

to a neat BF3-Et2O standard at 0.0 ppm. 77Se/77Se{1H} NMR was referenced to neat Me2Se at 0.0

ppm. 31P/31P{1H} NMR was referenced to the aqueous solution of 85% H3PO4 at 0.0 ppm. 195Pt

NMR was referenced to the aqueous solution of Na2PtCl6; short pulse sequence and relaxation

delays (~ 0.1 – 0.2 sec) were generally used. Electrospray ionization (ESI) mass spectra were

recorded on an Agilent 6210 LC/MS-TOF mass spectrometer with ESI source. Elemental

analyses (C, H, N) were performed by Quantitative Technologies (Intertek), Whitehouse, NJ.

Figure SI-1. Numbering convention for icosahedral 1,2- and1,7-dicarba-closo-dodecaboranes.

Figure SI-2. Synthesis of carborane-based P,S ligands. Synthetic conditions: (i), (v), and (viii) S2Cl2, AlCl3, DCM, room temperature; then reduction with Zn powder in AcOH; (ii), (vi), and (ix) ClCH2CH2PPh2, MeCN, KtBuO, r. t.; (iii) NaH, DME, S8; (vii) n-BuLi, ether, 0 oC -> r.t., then 2 eq. MeI.




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9-thiol-m-carborane (I):

1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 3.40-1.30 (bm, 9H, cage-BH), 3.01 (s, 2H, cage-CH),

0.42 (q, 1H, SH, 2JH-B = 4Hz); 13C{1H} NMR (100.6 MHz, CD2Cl2, 30 °C): δ 55.6 (cage-CH);

11B (128.4 MHz, CD2Cl2, 30 oC, BF3-Et2O): δ – 2.5 (s, 1B, B-S), -6.0 (d, 1JB-H = 176 Hz, 2BH), -

9.2 (d, 1JB-H = 149 Hz, 1BH), -12.7 (d, 1JB-H = 171 Hz, 2BH), -14.0 (d, 1JB-H = 167 Hz, 2BH), -

17.6 (d, 1JB-H = 184 Hz, 1BH), -20.9 (d, 1JB-H = 188 Hz, 1BH).

1-thiol-m-carborane (II):

1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 3.52 (s, 1H, cage-CH), 3.11 (s, 1H, C-SH), 3.18-1.22

(bm, 10H, cage-BH); 11B NMR (128.4 MHz, CD2Cl2, 30 °C, BF3-Et2O): δ -2.6 (d, 1JB-H= 165

Hz, 1 BH), -9.4 (d, 1JB-H= 185 Hz, 2 BH), -10.8 (d, 1JB-H= 168 Hz, 3 BH), -13.7 (d, 1JB-H= 166

Hz, 2 BH), -14.2 (d, 1JB-H= 183 Hz, 2 BH); 13C NMR (100.6 MHz, CD2Cl2, 30 °C): 57.5 (s, 1C,

cage-CH), 65.1 (s, 1C, cage-CSH).

9-thiol-o-carborane (III):

1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 3.64 (s, 1H, cage-CH), 3.48 (s, 1H, cage-CH), 3.10-

1.10 (bm, 9H, cage-BH), 0.38 (bs, 1H, SH); 13C{1H} NMR (100.6 MHz, CD2Cl2, 30 °C): δ

54.5 (cage-CH), 48.0 (cage-CH); 11B (128.4 MHz, CD2Cl2, 30 oC, BF3-Et2O): δ 4.9 (s, 1B, B-S),

1.3 (d, 1JB-H = 144 Hz, 1BH), -7.8 (d, 1JB-H = 153 Hz, 2BH), -13.0 (d, 1JB-H = 148 Hz, 2BH), -

14.0 (d, 1JB-H = 132 Hz, 2BH), -15.0 (d, 1JB-H = 165 Hz, 1BH).

9-thiol-1,2-dimethyl-o-carborane (IV):

1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 3.20 - 1.10 (bm, 9H, cage-BH), 1.99 (s, 3H, CH3), 1.95

(s, 3H, CH3), 0.24 (q, 1H, SH, 2JH-B = 4Hz); 13C{1H} NMR (100.6 MHz, CD2Cl2, 30 °C): δ

73.7 (cage-C), 66.9 (cage-C), 23.8 (CH3), 22.4 (CH3); 11B (128.4 MHz, CD2Cl2, 30 oC, BF3-

Et2O): δ 1.6 (s, 1B, B-S), - 5.1 (d, 1JB-H = 144 Hz, 1BH), -8.0 to -14.0 (m, 8BH).




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B. General procedure for synthesis of ligands 1a, 1c, 1d, 1e and 1f:

To a stirring solution of thiol (5 mmol) in 30 mL of dry acetonitrile under nitrogen was slowly

added potassium tert-butoxide (KtBuO) (0.57 g, 5.1 mmol). The reaction mixture was left

stirring for 5 minutes, after which 1-Chloro-2-diphenylphosphinoethane (1.25 g, 5 mmol) was

added and the reaction was left stirring for 12 hours at room temperature. All further

manipulations were performed in the air. The solution was filtered through a fine fritted funnel

filled with a layer of Celite™ and the solvent was removed under vacuum. The residue was

chromatographed on silica column with dichloromethane/hexanes mixtures followed by

recrystallization from cold pentane (-20 ˚C) to afford analytically pure ligands as crystalline

white solids.

Ligand 1a (yield = 92%): 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.41-7.34 (m, 4H, ArH),

7.32-7.23 (m, 6H, ArH), 3.40-1.20 (bm, 9H, cage-BH), 2.95 (s, 2H, cage-CH), 2.56 (bm, 2H,

SCH2), 2.32 (m, 2H, PCH2); 13C{1H} NMR (100.6 MHz, CD2Cl2, 30 °C): δ 138.8 (d, ArC, JC-P

= 14 Hz), 133.4 (d, ArC, JC-P = 19 Hz), 129.2 (s, ArC), 129.0 (d, ArC, JC-P = 7 Hz), 54.9 (s,

cage-CH), 31.3 (d, AliphC, JC-P = 15 Hz), 29.9 (d, AliphC, JC-P = 24 Hz); 11B (128.4 MHz,

CD2Cl2, 30 oC, BF3-Et2O): δ – 0.7 (s, 1B, B-S), -7.7 (d, 1JB-H = 164 Hz, 2BH), -11.0 (d, 1JB-H =

155 Hz, 1BH), -14.2 (d, 1JB-H = 104 Hz, 2BH), -15.0 (d, 1JB-H = 111 Hz, 2BH), -18.5 (d, 1JB-H =

181 Hz, 1BH), -21.5 (d, 1JB-H = 184 Hz, 1BH); 31P{1H} NMR (162.0 MHz, CD2Cl2, 30 °C): δ -

16.3 (s). Calculated for C16H25B10PS: C, 49.46; H, 6.49; found: C, 49.80; H, 6.48. Single crystals

suitable for X-ray diffraction studies were grown by slow evaporation from n-pentane in a NMR

tube.

Ligand 1c (yield = 90%): 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.43-7.34 (m, 4H, ArH),

7.34-7.25 (m, 6H, ArH), 3.59 (s, 1H, cage-CH), 3.50 (m, 1H, cage-CH), 3.10-1.30 (bm, 9H,




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cage-BH), 2.49 (bm, 2H, PCH2), 2.29 (m, 2H, SCH2); 13C{1H} NMR (100.6 MHz, CD2Cl2, 30

°C): δ 138.9 (d, ArC, JC-P = 14 Hz), 133.3 (d, ArC, JC-P = 18 Hz), 129.2 (s, ArC), 129.1 (d,

ArC, JC-P = 6 Hz), 53.9 (s, cage-CH), 48.6 (s, cage-CH), 33.4 (d, AliphC, JC-P = 16 Hz), 29.6 (d,

AliphC, JC-P = 23 Hz); 11B (128.4 MHz, CD2Cl2, 30 oC, BF3-Et2O): δ 7.4 (s, 1B-S), -2.4 (d, 1JB-

H = 158 Hz, 1BH), -8.6 (d, 1JB-H = 156 Hz, 2BH), -11.6 to -17.7 (m, 6BH); 31P{1H} NMR (162.0

MHz, CD2Cl2, 30 °C): δ - 16.3 (s). Calculated for C16H25B10PS: C, 49.46; H, 6.49; found: C,

49.46; H, 6.22. Single crystals suitable for X-ray diffraction studies were grown by slow

evaporation from n-pentane in a NMR tube.

Ligand 1d (yield = 84%): 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.43-7.34 (m, 4H, ArH),

7.33-7.25 (m, 6H, ArH), 3.19-1.12 (bm, 9H, cage-BH), 2.46 (bm, 2H, PCH2), 2.27 (m, 2H,

SCH2), 1.96 (bs, 6H, CH3); 13C{1H} NMR (100.6 MHz, CD2Cl2, 30 °C): δ 139.0 (d, ArC, JC-P =

14 Hz), 133.3 (d, ArC, JC-P = 19 Hz), 129.2 (s, ArC), 129.0 (d, ArC, JC-P = 7 Hz), 72.9 (s, cage-

C), 67.4 (s, cage-C), 31.4 (d, AliphC, JC-P = 14 Hz), 29.6 (d, AliphC, JC-P = 23 Hz), 23.8 (s,

AliphCH3), 22.5 (s, AliphCH3); 11B (128.4 MHz, CD2Cl2, 30 oC, BF3-Et2O): δ 3.9 (s, 1B-S), -

6.2 (d, 1JB-H = 151 Hz, 1BH), -8.2 to -14.5 (m, 8BH); 31P{1H} NMR (162.0 MHz, CD2Cl2, 30

°C): δ - 16.3 (s). Calculated for C18H29B10PS: C, 51.90; H, 7.02; found: C, 51.87; H, 6.76. Single

crystals suitable for X-ray diffraction studies were grown by slow evaporation from n-pentane in

a NMR tube.

Ligand 1e (yield = 93%): 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.55-7.21 (m, 10H, ArH),

2.59 (m, 2H, alkyl-CH), 2.31 (m, 2H, alkyl-CH), 1.26 (s, 9H, CH); 13C{1H} NMR (100.6 MHz,

CD2Cl2, 30 °C): δ 139.0 (d, ArC, JC-P = 14 Hz), 133.3 (d, ArC, JC-P = 19 Hz), 129.2 (d, ArC,

JC-P = 16 Hz), 129.0 (s, ArC), 43.0 (s, C(CH3)3), 31.4 (s, C(CH3)3), 29.4 (d, AliphC, JC-P = 14




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Hz), 25.5 (d, AliphC, JC-P = 22 Hz); 31P {1H} NMR (162.0 MHz, CD2Cl2, 30 °C): δ - 16.2 (s).

Calculated for C18H23PS: C, 71.49; H, 7.61; found: C, 71.83; H, 7.91.

Ligand 1f (yield = 95%): 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.47-7.28 (m, 10H, ArH),

2.56 (m, 2H, alkyl-CH), 2.28 (m, 2H, alkyl-CH), 1.97 (bd, 3H, AdH), 1.78 (d, 6H, AdH), 1.65

(q, 6H, AdH); 13C{1H} NMR (100.6 MHz, CD2Cl2, 30 °C): δ 138.9 (d, ArC, JC-P = 14 Hz),

133.3 (d, ArC, JC-P = 19 Hz), 129.3 (s, ArC), 129.0 (s, ArC, JC-P = 7 Hz), 45.3 (s, CSAd), 44.2

(s, CH2Ad), 36.9 (s, CH2Ad), 30.5 (s, CHAd), 30.0 (d, AliphC, JC-P = 14 Hz), 22.8 (d, AliphC,

JC-P = 22 Hz); 31P {1H} NMR (162.0 MHz, CD2Cl2, 30 °C): δ - 16.3 (s). Calculated for

C24H29PS: C, 75.75; H, 7.68; found: C, 75.61; H, 7.74.

C. Synthesis of ligand 1b: (2-chloroethyl)-diphenylphosphine (0.7 grams, 2.8 mmoles),

potassium carbonate (0.4 grams, 2.9 mmoles) and II (0.5 grams, 2.8 mmoles) were mixed in 15

mL of dry acetonitrile in a 50 mL Schlenk flask. The solution was degassed under N2 and then

heated under reflux for 12 hours. All further manipulations were performed in the air. Resulting

suspension was filtered through a layer of Celite™, evaporated in vacuo and purified on a silica

column with 6:4 mixture of dichloromethane and hexanes to afford analytically pure ligand 1b as

a colorless oil in 78% yield.

Ligand 1b: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.43-7.35 (m, 4H, ArH), 7.35-7.27 (m, 6H,

ArH), 3.60-1.20 (bm, 10H, cage-BH), 2.98 (s, 1H, cage-CH), 2.79 (m, 2H, SCH2), 2.24 (m, 2H,

PCH2); 13C{1H} NMR (100.6 MHz, CD2Cl2, 30 °C): δ 138.1 (d, ArC, JC-P = 14 Hz), 133.2 (d,

ArC, JC-P = 19 Hz), 129.6 (s, ArC), 129.2 (d, ArC, JC-P = 7 Hz), 73.3 (s, cage-CS), 56.4 (s,

cage-CH), 33.7 (d, AliphC, JC-P = 23 Hz), 27.9 (d, AliphC, JC-P = 16 Hz); 11B (128.4 MHz,

CD2Cl2, 30 oC, BF3-Et2O): δ – 4.5 (d, 1BH, 1JB-H = 156 Hz), -11.2 (d, 1JB-H = 168 Hz, 2BH), -

11.6 (d, 1JB-H = 142 Hz, 3BH), -14.3 (d, 1JB-H = 154 Hz, 2BH), -15.5 (d, 1JB-H = 174 Hz, 2BH);




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31P{1H} NMR (162.0 MHz, CD2Cl2, 30 °C): δ - 16.3 (s). Calculated for C16H25B10PS: C, 49.46;

H, 6.49; found: C, 49.21; H, 6.55.

D. General procedure for addition of 1 equivalent of P, S ligand to Pt(cod)Cl2.

A solution of ligand (0.125 mmol) in CH2Cl2 (5 mL) was added slowly dropwise to a solution of

[Pt(cod)Cl2] (47 mg, 0.125 mmol, 1 eq.) in CH2Cl2 (5 mL) at room temperature. The solution

was allowed to stir for 5 min and a specific complexation motif of the P,S ligand was confirmed

via in situ 31P/31P{1H} and other NMR techniques. 2a, 2c, 2d were purified as follows: solvent

was evaporated in vacuo and the oily residues were triturated three times with hexanes (ca. 5 mL

each time). The resulting oily substances were dried in vacuo to afford solid products, which

were subjected to analytical characterization. For complexes characterized by NMR in situ

CD2Cl2 was used instead of CH2Cl2.

2a: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.84-7.65 (m, 3H, ArH), 7.55-7.09 (m, 7H, ArH),

3.19 (s, 2H, cage-CH), 3.34-1.46 (m, 13H, cage-BH, alkyl-CH); 11B NMR (128.4 MHz, CD2Cl2,

30 °C, BF3-Et2O): δ -4.7 (s, 1B, SB), -7.4 (d, 1JB-H= 82 Hz, 2BH), -9.3 to -20.91 (m, 7BH); 31P

{1H} NMR (162.0 MHz, CD2Cl2, 30 °C): δ 40.8 (s, JP-Pt = 3625 Hz). HRMS (ESI): m/z calcd for

C16H25B10ClPPtS [M-Cl]+: 618.1754, found: 618.1760. Calculated for

C16B10H25Cl2PPtS·¼C6H14: C, 31.09; H, 4.25; found: C, 31.10; H, 4.30. Single crystals suitable

for X-ray diffraction studies were grown by slow evaporation from CH2Cl2 in a NMR tube.

2c: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.84-7.64 (m, 3H, ArH), 7.62-7.07 (m, 7H, ArH),

4.35 (s, 1H, cage-CH), 4.10 (s, 1H, cage-CH), 2.62 (bs, 2H, alkyl-CH), 2.50 (bs, 2H, alkyl-CH),

3.27-1.30 (m, 9H, cage-BH); 11B NMR (128.4 MHz, CD2Cl2, 30 °C, BF3-Et2O): δ -1.3 (s, 1B,

B-S), -4.6 (d, 1JB-H= 70 Hz, 1BH), -10.4 (d, 1JB-H= 75 Hz, 2BH), -12.0 to -20.8 (m, 6BH); 31P

{1H} NMR (162.0 MHz, CD2Cl2, 30 °C): δ 41.1 (s, JP-Pt = 3634 Hz). HRMS (ESI): m/z calcd for




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C16H25B10ClPPtS [M-Cl]+: 618.1754, found: 618.1709. Calculated for

C16B10H25Cl2PPtS·¼C6H14: C, 31.09; H, 4.25; found: C, 31.19; H, 4.17. Single crystals suitable

for X-ray diffraction studies were grown by slow evaporation from CH2Cl2 in a NMR tube.

2d: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.91-7.64 (m, 3H, ArH), 7.61-7.06 (m, 7H, ArH)

3.22-1.43 (bm, 13H, cage-BH, alkyl-CH), 2.05 (s, 3H, BCH), 1.98 (s, 3H, BCH); 11B NMR

(128.4 MHz, CD2Cl2, 30 °C, BF3-Et2O): δ -0.2 (s, 1B, B-S), -5.1 to -14.6 (bm, 9BH); 31P {1H}

NMR (160.2 MHz, CD2Cl2, 30 °C): δ 40.9 (s, JP-Pt = 3642 Hz). HRMS (ESI): m/z calcd for

C18H29B10ClPPtS [M-Cl]+: 646.2067, found: 646.2051. Calculated for C18B10H29Cl2PPtS: C,

31.67; H, 4.28; found: C, 32.06; H, 4.30. Single crystals suitable for X-ray diffraction studies

were grown by slow evaporation from CH2Cl2 in a NMR tube.

2e: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 8.02-7.85 (m, 2H, ArH), 7.72-7.21 (m, 8H, ArH),

2.98-2.23 (m, 4H, alkyl-CH), 1.47 (s, 9H, CH); 31P {1H} NMR (100.6 MHz, CD2Cl2, 30 °C): δ

40.1 (s, JP-Pt= 3600 Hz). HRMS (ESI): m/z calcd for C18H23ClPPtS [M-Cl]+: 532.0594, found:

532.0547.

2f: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 8.00-7.11 (m, 10H, ArH), 3.01-2.33 (bm, 4H, alkyl-

CH), 2.27-2.14 (bs, 3H, AdH), 2.13-1.83 (bs, 6H, AdH), 1.64 (bs, 6H, AdH); 31P {1H} NMR

(162.0 MHz, CD2Cl2, 30 °C): δ 40.7 (s, JP-Pt= 3608 Hz). HRMS (ESI): m/z calcd for

C24H29ClPPtS [M-Cl]+: 610.1064, found: 610.1050. Single crystals of X-Ray quality were grown

by slow evaporation from dichloromethane in a NMR tube.




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2g: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 8.15 (d, 1H, ArH), 7.93 (m, 4H, ArH), 7.60 (m, 6H,

ArH), 7.19 (s, 1H, ArH), 7.17 (s, 1H, ArH), 2.97 (m, 1H, Alkyl-CH), 2.73 (m, 2H, Alkyl-CH), δ

2.61 (s, 3H, Alkyl-CH), δ 2.52 (m, 1H, Alkyl-CH), 2.39 (s, 3H, Alkyl-CH); 31P{1H} NMR

(162.0 MHz, CD2Cl2, 30 °C) δ 39.7 (s, JP-Pt = 3604 Hz). HRMS (ESI): m/z calcd for

C22H23ClPPtS [M-Cl]+: 580.0594, found: 580.0573. Single crystals of X-Ray quality were grown

by slow evaporation from dichloromethane in a NMR tube.

E. General procedure for preparation of bisligated complexes.

A solution of P,S ligand (0.125 mmol) in CH2Cl2 (3 mL) was added slowly dropwise to a

solution of mono addition products (section 1D) at room temperature. The solution was allowed

to stir for 5 min, and a specific complexation motif of the P,S ligand was confirmed via in situ

31P/31P{1H} and other NMR techniques. 3a, 2b, 3c and 3d were purified as follows: solvent was

evaporated in vacuo and the resulting oily residues were triturated three times with hexanes (ca.

5 mL each time). The resulting oily substances were dried in vacuo to afford solid products,

which were subjected to analytical characterization. For complexes characterized by NMR in situ


3a: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.92-6.91 (bm, 20H, ArH), 3.30 (bs, 4H, cage-

CH), 3.40-1.27 (bm, 26H, cage-BH, alkyl CH); 11B (128.4 MHz, CD2Cl2, 30 oC, BF3-Et2O): δ -

1.9 (s, 1B, B-S), δ - 3.6 (s, 1B, B-S), -7.7 (d, 1JB-H = 155 Hz, 2BH), -11.2 (d, 1JB-H = 153 Hz,

2BH), -12.5 to – 24.1 (bm, 14BH); 31P {1H} NMR (162.0 MHz, CD2Cl2, 30 °C): δ 45.2 (bs, 1JP-

Pt=3528 Hz), 9.8 (bs, 1JP-Pt=3245 Hz); (162.0 MHz, CD2Cl2, - 5 °C): δ 45.2 (d, 2JP-P=13 Hz 1JP-

Pt=3525 Hz), 9.9 (d, 2JP-P=14 Hz, 1JP-Pt=3255 Hz). HRMS (ESI): m/z calcd for C32B20H50ClP2PtS2

[M-Cl]+: 1006.4172, found: 1006.4147. Calculated for C32B20H50Cl2P2PtS2: C, 36.85; H, 4.83;

found: C, 37.11; H, 4.75.




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2b: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.94-7.10 (m, 20H, ArH), 2.97 (s, 2H, cage-CH),

2.85 (m, 4H, alkyl-CH), 2.40 (m, 4H, alkyl-CH), 3.27-1.30 (m, 20H, cage-BH); 11B NMR (128.4

MHz, CD2Cl2, 30 °C, BF3-Et2O): δ -4.6 (d, 2BH, 1JB-H= 162 Hz), -7.7 (d, 1JB-H= 164 Hz, 2BH), -

-12.9 to -19.7 (m, 16BH); 31P {1H} NMR (162.0 MHz, CD2Cl2, 30 °C): δ 7.3 (s, JP-Pt = 3638

Hz). HRMS (ESI): m/z calcd for C32B20H50ClP2PtS2 [M-Cl]+: 1006.4172, found: 1006.4167.

Calculated for C32B20H50Cl2P2PtS2: C, 36.85; H, 4.83; found: C, 36.99; H, 4.65.

3c: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.77-6.83 (bm, 20H, ArH), 3.40-1.21 (bm, 30H,

cage-BH, cage-CH, Alkyl-CH); 11B (128.4 MHz, CD2Cl2, 30 oC, BF3-Et2O): δ 6.3 (s, 1B, B-S),

2.8 (s, 1B, B-S), -2.9 (d, 1JB-H = 144 Hz, 2BH), -9.0 (d, 1JB-H = 144 Hz, 2BH), -11.1 to – 18.2

(bm, 14BH); 31P {1H} NMR (162.0 MHz, CD2Cl2, 30 °C): δ 45.3 (bs, 1JP-Pt=3541 Hz), 9.8 (bs,

1JP-Pt=3216 Hz); (162.0 MHz, CD2Cl2, 5 °C): δ 45.3 (d, 2JP-P=13 Hz 1JP-Pt=3555 Hz), 9.9 (d, 2JP-

P=14 Hz, 1JP-Pt=3210 Hz). HRMS (ESI): m/z calcd for C32B20H50ClP2PtS2 [M-Cl]+: 1006.4172,

found: 1006.4177. Calculated for C32B20H50Cl2P2PtS2: C, 36.85; H, 4.83; found: C, 37.24; H,

4.91.

3d: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.81 - 6.87 (m, 20H, ArH), 3.31 - 1.52 (bm, 18H,

cage-BH), 2.65 (bs, 4H, Alkyl-CH), 2.47 (s, 4H, cage-CH), 2.07 – 1.97 (bm, 12H, cage-CH3);

11B (128.4 MHz, CD2Cl2, 30 oC, BF3-Et2O): δ 2.9 (s, 1B, B-S), δ 0.3 (s, 1B, B-S), -6.9 (d, 1JB-H =

154 Hz, 2BH), -8.5 to – 15.3 (bm, 16BH); 31P {1H} NMR (162.0 MHz, CD2Cl2, 30 °C): δ 45.1

(bs, 1JP-Pt=3530 Hz), 9.8 (bs, 1JP-Pt=3244 Hz); (162.0 MHz, CD2Cl2, 5 °C): δ 45.2 (d, 2JP-P=14

Hz 1JP-Pt=3528 Hz), 9.8 (d, 2JP-P=14 Hz, 1JP-Pt=3238 Hz). HRMS (ESI): m/z calcd for C36

B20H58P2ClPtS2 [M-Cl]+: 1062.4798, found: 1062.4835. Calculated for C36B20H58Cl2P2PtS2: C,

39.34; H, 5.32; found: C, 40.17; H, 5.56.




13

3e: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.89-7.14 (bm, 20H, ArH), 2.96 – 2.59 (bm, 8H,

Alkyl-CH), 1.43 (bs, 18H, Alkyl-CH); 31P {1H} NMR (162.0 MHz, CD2Cl2, - 45 °C): δ 42.8 (bs,

1JP-Pt=3601 Hz), 10.5 (bs, 1JP-Pt=3194 Hz). HRMS (ESI): m/z calcd for C36H46ClP2PtS2 [M-Cl]+:

834.1852, found: 834.1844.

3f: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.79-7.19 (m, 20H, ArH), 2.97-2.63 (bm, 8H,

Alkyl-CH), 2.07 (bs, 6H, Alkyl-CH), 2.01 (bs, 12H, Alkyl-CH) 1.78 - 1.61 (bm, 12H, alkyl-CH);

31P {1H} NMR (162.0 MHz, CD2Cl2, - 30 °C): δ 42.0 (bs, 1JP-Pt=3590 Hz), 10.5 (bs, 1JP-Pt=3240

Hz). HRMS (ESI): m/z calcd for C48H56ClP2PtS2 [M-Cl]+: 990.2791, found: 990.2823.

3g: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.52 (m, 4H, ArH), 7.43 (m, 8H, ArH), 7.33 (m,

8H, ArH), 7.13 (m, 2H, ArH), 7.09 (s, 2H, ArH), 6.97 (m, 2H, ArH), 2.92 (m, 4H, Alkyl-Alkyl-

CH), 2.71 (m, 4H, Alkyl-CH), 2.39 (s, 6H, Alkyl-CH), 2.36 (s, 6H, Alkyl-CH). 31P{1H} NMR

(162.0 MHz, CD2Cl2, 30 °C) δ 11.13 (bs). HRMS (ESI): m/z calcd for C44H46ClP2PtS2 [M-Cl]+:

930.1852, found: 930.1812.

F. General procedure for mono-abstraction of Cl- from bisligated complexes.

To a solution of a bisligated complex (0.125 mmoles, see section 1E) NaBArF (0.125 mmoles,

111 mg, 1 equiv) dissolved in 3 mL of CH2Cl2 was added and the cloudy mixture was left




14

vigorously stirring for 30 min, where in situ 31P/31P{1H} and other NMR techniques confirmed

quantitative mono-abstraction. 3a', 3b, 3c' and 3d' were purified as follows: the solutions were

filtered through a layer of Celite™, filtrate was evaporated in vacuo and the resulting oily

residues were triturated three times with hexanes (ca. 5 mL each time). The resulting oily

substances were dried in vacuo to afford solid products, which were subjected to analytical

characterization. For complexes characterized by NMR in situ CD2Cl2 was used instead of

CH2Cl2.

3a': 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.74 (bs, 8H, BArF ArH), 7.55 (bs, 4H, BArF

ArH), 7.62-7.04 (bm, 20H, ArH), 3.62-1.31 (bm, 30H, cage-H, alkyl CH); 11B (128.4 MHz,

CD2Cl2, 30 oC, BF3-Et2O): δ - 1.4 (s, 1B, B-S), δ - 4.2 (s, 1B, B-S), -7.7 (d, 1JB-H = 166 Hz,

2BH), -7.6 (m, 1B, BArF), -11.3 (d, 1JB-H = 155 Hz, 2BH), -12.5 to – 25.2 (bm, 14BH); 31P

{1H} NMR (162.0 MHz, CD2Cl2, 30 °C): δ 44.9 (bs, 1JP-Pt=3513 Hz), 9.9 (bs, 1JP-Pt=3229 Hz);

(162.0 MHz, CD2Cl2, - 5 °C): δ 45.1 (d, 2JP-P=13 Hz 1JP-Pt=3534 Hz), 9.9 (d, 2JP-P=13 Hz, 1JP-

Pt=3237 Hz). HRMS (ESI): m/z calcd for C64B21H62F24P2PtS2 [M-Cl]+: 1834.5132, found:

1834.5178. Calculated for C64B21H62ClF24P2PtS2: C, 41.09; H, 3.34; found: C, 41.11; H, 3.38.

3b: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.82-7.14 (m, 32H, ArH), 3.38-1.21 (bm, 30H,

cage-BH, cage-CH, Alkyl-CH); 11B NMR (128.4 MHz, CD2Cl2, 30 °C, BF3-Et2O): δ - 4.6 (d,

1JB-H= 165 Hz, BH), -7.2 (s, 1B, BArF), -11.0 (d, 1JB-H= 156 Hz, BH), -13.72 (d, 1JB-H= 159 Hz,

BH), -15.1 (d, 1JB-H= 180 Hz, BH), -17.5 (d, 1JB-H= 185 Hz, BH); 31P {1H} NMR (162.0 MHz,

CD2Cl2, 30 °C): δ 42.5 (d, 2JP-P=14 Hz, 1JP-Pt = 3452 Hz), 10.1 (d, 2JP-P=14 Hz, 1JP-Pt = 3365 Hz).

HRMS (ESI): m/z calcd for C64B21H62F24P2PtS2 [M-Cl]+: 1834.5132, found: 1834.5083.

Calculated for C64B21H62ClF24P2PtS2: C, 41.09; H, 3.34; found: C, 41.13; H, 3.37.




15

3c': 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.73 (m, 8H, BArF-H), 7.64-7.09 (m, 20H, ArH),

7.56 (s, 4H, BArF-H), 4.16-3.38 (bm, 4H, cage-CH), 3.31 – 1.15 (bm, 26H, Alkyl-CH and cage-

BH); 11B (128.4 MHz, CD2Cl2, 30 oC, BF3-Et2O): δ 5.5 (s, 1B, B-S), δ 2.3 (s, 1B, B-S), -3.4 (d,

1JB-H = 150 Hz, 2BH), -7.6 (m, 1B, BArF), -10.0 (d, 1JB-H = 152 Hz, 2BH), -12.5 to – 20.9 (bm,

14BH); 31P {1H} NMR (162.0 MHz, CD2Cl2, 30 °C): δ 45.0 (bs, 1JP-Pt=3539 Hz), 9.9 (bs, 1JP-

Pt=3232 Hz). HRMS (ESI): m/z calcd for C64B21H62F24P2PtS2 [M-Cl]+: 1834.5132, found:

1834.5139. Calculated for C64B21H62ClF24P2PtS2: C, 41.09; H, 3.34; found: C, 40.95; H, 3.33.

3d': 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.74 (m, 8H, BArF-H), 7.69-7.06 (m, 20H, ArH),

7.56 (s, 4H, BArF-H), 3.51 – 1.02 (bm, 26H, Alkyl-CH and cage-BH), 2.03 (bs, 12H, cage-

CCH3); 11B (128.4 MHz, CD2Cl2, 30 oC, BF3-Et2O): δ 3.8 (s, 1B, B-S), δ 0.9 (s, 1B, B-S), -6.2

(d, 1JB-H = 158 Hz, 2BH), -7.2 (m, 1B, BArF), -7.5 to – 15.8 (bm, 14BH); 31P {1H} NMR (162.0

MHz, CD2Cl2, 30 °C): δ 44.9 (bs, 1JP-Pt=3543 Hz), 9.8 (bs, 1JP-Pt=3217 Hz). Calculated for

C68B21H70ClF24P2PtS2: C, 42.39; H, 3.66; found: C, 42.12; H, 3.72.

3e': 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 8.02-6.91 (bm, 32H, ArH), 3.70 – 1.57 (bm, 26H,

AlkH); 31P {1H} NMR (162.0 MHz, CD2Cl2, 30 °C): δ 42.5 (bs, 1JP-Pt=3574 Hz), 10.1 (bs, 1JP-

Pt=3186 Hz); (162.0 MHz, CD2Cl2, - 45 °C): δ 42.0 (d, 2JP-P=12 Hz 1JP-Pt=3592 Hz), 10.4 (d, 2JP-




16

P=15 Hz, 1JP-Pt=3192 Hz). HRMS (ESI): m/z calcd for C36H46ClP2PtS2 [M-BArF]+: 834.1852,

found: 834.1840.

3i: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.82-6.94 (bm, 34H, ArH), 3.24 – 2.46 (bm, 8H,

AlkH); 19F NMR (376.5 MHz, CD2Cl2, 30 °C) δ -62.9 (m, 24F, BArF), -130.1 (m, 2F, ArF), -

133.8 (m, 2F, ArF), -134.4 (m, 2F, ArF), -138.0 (m, 2F, ArF). 31P {1H} NMR (162.0 MHz,

CD2Cl2, 30 °C): δ 43.4 (d, 2JP-P=15 Hz 1JP-Pt=3454 Hz), 9.9 (d, 2JP-P=15 Hz, 1JP-Pt=3369 Hz).

HRMS (ESI): m/z calcd for C40H30ClF8P2PtS2 [M+BArF]+: 1018.0473, found: 1018.0514. Single

crystals suitable for X-Ray studies of the analogous complex 3i-BF4 (obtained from

monoabstraction reaction with AgBF4) were grown by slow diffusion of diethyl ether, layered on

top of a dichloromethane solution of 3i-BF4 in a NMR tube.

G. General procedure for full abstraction of Cl- from bisligated complexes.

To a solution of a bisligated complex (0.125 mmoles, see section 1E) AgBF4 (0.25 mmoles, 48

mg, 1 equiv) was added and the cloudy mixture was left vigorously stirring for 1 hour. In situ

31P/31P{1H} and other NMR techniques were used to confirm quantitative abstractions. 4a-d

were purified as follows: the solutions were filtered through a layer of Celite™, filtrate was

evaporated in vacuo and the resulting oily residues were triturated three times with hexanes (ca.

5 mL each time). The resulting oily substances were dried in vacuo to afford solid products,

which were subjected to analytical characterization. For complexes characterized by NMR in situ


4a: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.76-6.98 (bm, 20H, ArH), 3.58-1.26 (bm, 30H,

cage-BH, cage-CH, Alkyl-CH); 11B (128.4 MHz, CD2Cl2, 30 oC, BF3-Et2O): - 2.2 (s, 2B, BF4), δ

- 4.3 (s, 2B, B-S), - 5.5 to - 24.8 (bm, 18BH); 31P{1H} NMR (100.6 MHz, CD2Cl2, 30 °C): δ 48.2

(s, 1JP-Pt=3135). HRMS (ESI): m/z calcd for C32B20H50P2PtS2 [M-2BF4]2+: 485.7242, found:




17

485.7267. Calculated for C32B22H50F8P2PtS2: C, 33.55; H, 4.40; found: C, 35.78; H, 4.37. Single

crystals suitable for X-Ray studies were grown by slow diffusion of diethyl ether, layered on top

of a dichloromethane solution of 4a in a NMR tube.

4b: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.96-6.81 (m, 20H, ArH), 3.95 (s, 2H, cage-CH),

3.78-1.02 (bm, 28H, cage-BH and alkyl-CH); 11B (128.4 MHz, CD2Cl2, 30 oC, BF3-Et2O): δ -

2.3 (s, 2B, BF4), - 3.6 to - 23.8 (bm, 20BH); 31P{1H} NMR (100.6 MHz, CD2Cl2, 30 °C): δ 43.2

(s, 1JP-Pt=3207). HRMS (ESI): m/z calcd for C32B20H50ClP2PtS2 [M-2BF4+Cl]+: 1006.4172,

found: 1006.4129. Calculated for C32B22H50F8P2PtS2: C, 33.55; H, 4.40; found: C, 33.62; H,

4.39. Single crystals suitable for X-Ray studies were grown by slow diffusion of diethyl ether,

layered on top of a dichloromethane solution of 4b in a NMR tube.

4c: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.74-6.91 (bm, 20H, ArH), 3.58-1.26 (bm, 30H,

cage-BH, cage-CH, Alkyl-CH); 11B (128.4 MHz, CD2Cl2, 30 oC, BF3-Et2O): δ 1.2 (s, 2B, B-S),

- 2.4 (s, 2B, BF4), - 4.3 (d, 1JB-H = 116 Hz, 2BH), - 7.9 to - 24.7 (bm, 16BH); 31P{1H} NMR

(100.6 MHz, CD2Cl2, 30 °C): δ 48.5 (s, 1JP-Pt=3119). HRMS (ESI): m/z calcd for C32

B20H50P2PtS2 [M-2BF4]2+: 485.7242, found: 485.7231. Calculated for C32B22H50F8P2PtS2: C,

33.55; H, 4.40; found: C, 32.74; H, 4.29. Single crystals suitable for X-Ray studies were grown

by slow diffusion of diethyl ether, layered on top of a dichloromethane solution of 4c in a NMR

tube.

4d: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 7.96-6.93 (m, 20H, ArH), 3.56-1.32 (m, 18H, cage-

BH, Alkyl-CH), 2.16 (s, 6H, cage-CCH3), 2.08 (bm, 6H, cage-CCH3); 11B (128.4 MHz, CD2Cl2,

30 oC, BF3-Et2O): δ 0.1 (s, 2B, B-S), - 2.4 (s, 2B, BF4), - 4.8 to - 15.6 (bm, 18BH); 31P{1H}

NMR (100.6 MHz, CD2Cl2, 30 °C): δ 48.3 (s, 1JP-Pt=3132). HRMS (ESI): m/z calcd for C36

B20H58P2PtS2 [M-2BF4]2+: 513.7552, found: 513.7518. Calculated for C36B22H58F8P2PtS2: C,




18

35.98; H, 4.86; found: C, 36.21; H, 5.18. Single crystals suitable for X-Ray studies were grown

by slow diffusion of diethyl ether, layered on top of a dichloromethane solution of 4d in a NMR

tube.

4e: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 8.15-6.64 (m, 20H, ArH), 3.82-3.21 (bs, 4H, alkyl-

CH), 2.98 – 2.49 (bs, 4H, alkyl-CH), 1.46 (s, 18H, CH); 31P {1H} NMR (162.0 MHz, CD2Cl2, 30

°C): δ 45.0 (s, 1JP-Pt= 3115 Hz). HRMS (ESI): m/z calcd for C36H46ClP2PtS2 [M-2BF4+Cl]+:

834.1852, found: 834.1844. Single crystals suitable for X-Ray studies were grown by slow

diffusion of diethyl ether, layered on top of a dichloromethane solution of 4e in a NMR tube.

4f: 1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 8.03 - 6.74 (bm, 20H, ArH), 3.48-2.37 (bm, 8H,

Alkyl-CH), 2.14 (bs, 6H, Alkyl-CH), 2.03 (bs, 12H, Alkyl-CH) 1.70 (bq, 12H, alkyl-CH); 31P

{1H} NMR (162.0 MHz, CD2Cl2, 30 °C): δ 45.3 (s, 1JP-Pt= 3120 Hz). HRMS (ESI): m/z calcd for

C48H56ClP2PtS2 [M-2BF4+Cl]+: 990.2791, found: 990.2729. Single crystals suitable for X-Ray

studies were grown by slow diffusion of diethyl ether, layered on top of a dichloromethane

solution of 4f in a NMR tube.




19

4g: 1H NMR (400.13 MHz, CD2Cl2, 30 °C): δ 7.75 (d, 2H, ArH), 7.52 (br, m, 20H, ArH), δ 7.37

(d, 2H, ArH), 6.99 (s, 2H, ArH), 3.14 (bm, 4H, Aliph-CH), 2.61 (bm, 4H, Aliph-CH), 2.38 (s,

6H, Aliph-CH), 1.88 (s, 6H, Aliph-CH). 31P{1H} NMR (162.0 MHz, CD2Cl2, 30 °C) δ 46.7 (s,

1JP-Pt = 3133 Hz). HRMS (ESI): m/z calcd for C44H46P2PtS2 [M-2BF4]2+: 447.6082, found:

447.6086. Single crystals suitable for X-Ray studies were grown by slow diffusion of diethyl

ether, layered on top of a dichloromethane solution of 4g in a NMR tube.

4h: 1H NMR (400.13 MHz, CD2Cl2, 30 °C): δ 7.84 – 7.18 (m, 30 ArH), δ 3.37 – 2.87 (m, 8

Aliph-H); 31P{1H} NMR (162.0 MHz, CD2Cl2, 30 °C): δ 45.9 (s, 1JP-Pt = 3140 Hz). HRMS (ESI):

m/z calcd for C40H38ClP2PtS2 [M-2BF4+Cl]+: 874.1226, found: 874.1248. Single crystals suitable

for X-Ray studies were grown by slow diffusion of diethyl ether, layered on top of a

dichloromethane solution of 4h in a NMR tube.

4i: 1H NMR (400.13 MHz, CD2Cl2, 30 °C): δ 7.71 – 7.33 (m, 22H, ArH), 3.25 (bm, 8H, Alkyl-

CH), 31P{1H} NMR (162.0 MHz, CD2Cl2, 30 °C) δ 46.9 (s, JP-Pt = 3231 Hz). 19F NMR (CD2Cl2,

376 MHz) δ -129.16 (m, 4F, ArF), -133.34 (m, 4F, ArF), δ -150.89 (s, 8F, BF4). HRMS (ESI):

m/z calcd for C40H30ClF8P2PtS2 [M-2BF4+Cl]+: 1018.0473, found: 1018.0527. Single crystals

suitable for X-Ray studies were grown by slow diffusion of diethyl ether, layered on top of a

dichloromethane solution of 4i in a NMR tube.

H. Representative Mixed-Ligand Experiment.

A solution of 1i (0.125 mmol) in d4-MeOD (2 mL) was added slowly dropwise to a suspension

of mono addition product 2a (section 1D) in CD2Cl2 (2 mL) at room temperature. The solution

was allowed to stir for 5 min, and a clean formation of a heteroligated product (6, see Figure SI-

9) was confirmed via in situ NMR techniques and HRMS.




20

6: 31P{1H} NMR (162.0 MHz, CD2Cl2, 30 °C) δ 47.3 (d, 1JP-Pt = 3486 Hz, 2JP-P = 13 Hz), 11.1 (d,

1JP-Pt = 3273 Hz, 2JP-P = 15 Hz); 11B (128.4 MHz, CD2Cl2, 30 oC, BF3-Et2O): δ - 1.7 (s, 1B, B-S),

- 3.3 to – 20.4 (bm, 9BH); 19F NMR (CD2Cl2, 376 MHz) δ -132.0 (m, 4F, ArF), -136.5 (m, 4F,

ArF). HRMS (ESI): m/z calcd for C38H50B10F4P2PtS2 [M-Cl]+: 1012.2322, found: 1012.2402.

I. Selenol Syntheses.

9-selenol-m-carborane (5a): To a solution of m-carborane (4.32 grams, 30 mmoles) in 75 mL of

dry dichloromethane under nitrogen AlCl3 (~ 4g) was added followed by the slow addition of

Se2Cl2 (3.45 grams, 15 mmoles). The reaction mixture was left stirring for 12 hours,

subsequently quenched with water and extracted with additional amounts of dichloromethane

and brine. The combined organic fractions were dried with Na2SO4, solvent was evaporated in

vacuo and the product was resuspended into anhydrous ethanol (100 mL). Portions of NaBH4 (~

2.4 grams total) were then slowly added to a vigorously stirring mixture for ~ 20 minutes

(Caution: it is recommended to perform this step in a large 500 mL Schlenk flask open to the air

under a positive stream of inert gas, to avoid any pressure build-ups from evolving H2 gas). The

reaction was subsequently slowly diluted with 100 mL of water, filtered through a layer of

Celite™ and acidified with a solution of 6M HCl (100 mL). The resulting solid was filtered out

of the solution on a glass frit and dried in vacuo. Crude selenol product was then passed through

a layer of silica with dichloromethane to afford the analytically pure selenol in 51% yield as a

yellowish solid. (Note: all purification and manipulations with 9-selenol-m-carborane were done

under ambient conditions, while long-term storage is recommended under inert atmosphere.)

1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 3.50-1.25 (bm, 9H, cage-BH), 3.06 (s, 2H, cage-CH), -

1.81 (bm, 1H, SeH, 1JH-Se = 56 Hz, 2JH-B = 4 Hz); 13C{1H} NMR (100.6 MHz, CD2Cl2, 30

°C): δ 56.7 (cage-CH); 11B (128.4 MHz, CD2Cl2, 30 oC, BF3-Et2O): δ – 6.6 (s, 2BH, 1JB-H = 168




21

Hz), -8.8 (s, 1B, B-Se), -9.7 (d, 1JB-H = 183 Hz, 1BH), -13.2 (d, 1JB-H = 156 Hz, 2BH), -14.3 (d,

1JB-H = 159 Hz, 2BH), -17.9 (d, 1JB-H = 184 Hz, 1BH), -20.5 (d, 1JB-H = 186 Hz, 1BH). );

77Se{1H} NMR (76.3 MHz, CD2Cl2, 30 °C, Me2Se): δ - 278 (q, 1SeH, 1JSe-B = 35 Hz). HRMS

(ESI): m/z calcd for C2B10H11Se [M-H]-: 223.1029, found: 223.1018. Calculated for C2B10H12Se:

C, 10.76; H, 5.42; found: C, 11.09; H, 5.32.

1-selenol-m-carborane (5b): A Schlenk flask filled with a solution of m-carborane (5.76 grams,

40 mmoles) in 100 mL of dry diethyl ether and purged under nitrogen was cooled on ice bath.

To this mixture n-BuLi (18 mL, 2.5M, 45 mmoles) was added slowly dropwise and the reaction

mixture was stirred for 30 minutes at 0 oC; then brought to room temperature and stirred for an

additional 1 hour. To this mixture elemental selenium (3.16 grams, 40 mmoles) was added and

left stirring at room temperature for 24 hours. The reaction mixture was subsequently quenched

with methanol and evaporated the solvent was evaporated in vacuo. The resulting solid was

suspended in a mixture of methanol (150 mL) and concentrated HCl (~ 5 mL) and stirred under a

stream of air for 12 hours. This suspension was dried in vacuo, redissolved in EtOH (100 mL)

and filtered. The filtrate was evaporated in vacuo and the resulting solid products were purified

via vacuum sublimation (to remove unreacted m-carborane, approx. 50 oC/1 mTorr). The

resulting yellow solid (diselenide) was reduced with NaBH4 by the same procedure to the one

used in the case of 9-selenol-m-carborane. This afforded analytically pure 1-selenol-m-carborane

in 38% yield. (Note: all purification and manipulations with 9-selenol-m-carborane were done

under ambient conditions, while long-term storage is recommended under inert atmosphere.)

1H NMR (400.1 MHz, CD2Cl2, 30 °C): δ 3.80-1.30 (bm, 10H, cage-BH), 3.04 (s, 1H, cage-CH),

- 2.04 (s, 1H, SeH); 13C{1H} NMR (100.6 MHz, CD2Cl2, 30 °C): δ 58.5 (cage-CH), 49.8 (cage-

CSe); 11B (128.4 MHz, CD2Cl2, 30 oC, BF3-Et2O): δ – 3.1 (s, 1BH, 1JB-H = 174 Hz), -9.7 (d, 1JB-H




22

= 173 Hz, 1BH), -10.6 (d, 1JB-H = 145 Hz, 4BH), -13.7 (d, 1JB-H = 183 Hz, 2BH), -14.4 (d, 1JB-H

= 198 Hz, 2BH); 77Se NMR (76.3 MHz, CD2Cl2, 30 °C, Me2Se): δ 347 (d, 1SeH, 1JSe-H = 51

Hz). HRMS (ESI): m/z calcd for C2B10H11Se [M-H]-: 223.1029, found: 223.1022. Calculated for

C2B10H12Se: C, 10.76; H, 5.42; found: C, 11.07; H, 5.59.

2. Additional NMR spectra.

Figure SI-3. Variable temperature a) 31P and b) 31P{1H} NMR spectra of 3a highlighting the

“windshield wiper” exchange processes.

Figure SI-4. 195Pt NMR (acquired in situ) of 1 eq. of 1b stirred for 5 minutes with 1eq. of

Pt(cod)Cl2 in CD2Cl2.




23

Figure SI-5. 195Pt NMR (acquired in situ) of 2 eq. of 1b stirred for 5 minutes with 1eq. of

Pt(cod)Cl2 in CD2Cl2.

Figure SI-6. 195Pt NMR of 3a (apparent broadness of the resonance confirms fluxionality

observed via other NMR techniques).

Figure SI-6. 195Pt NMR of 2a.

Figure SI-7. 195Pt NMR of 3b and 3a'.




24

Figure SI-8. 31P{1H} NMR of 3i.

Figure SI-9. Heteronuclear NMR spectra of 6.

3. Crystallographic structure determination and refinement details.

Single crystals suitable for X-ray diffraction studies were mounted using oil (Infenium V8512)

on a glass fiber. All measurements were made on Bruker APEX-II CCD with graphite-

monochromated Mo Kα or Cu Kα radiation. The data were collected at a temperature 100(2) K

using APEX2 Version 2.1-4 by Bruker (2007) detector and processed using SAINTPLUS

software (Bruker). The data were corrected using their respective linear absorption coefficients

(µ) before being corrected for Lorentz and polarization effects. The structures were solved by




25

direct methods and expanded using Fourier techniques. Neutral atom scattering factors were

taken from Cromer and Waber8. Anomalous dispersion effects were included in Fcalc9 the values

for Df’ and Df’’ were those of Creagh and McAuley.10 The values for the mass attenuation

coefficients are those of Creagh and Hubbell.11 All calculations related to these corrections were

performed using Bruker SHELXTL3 crystallographic software package. All explanations for A

and B alerts generated from CheckCif are discussed in the refine_special_details of the

corresponding cif files.

Crystal data and structure refinement for 1a (CCDC 824078). Identification code n0242 Empirical formula C16 H25 B10 P S Formula weight 388.49 Temperature 100(2) K Wavelength 1.54178 Å Crystal system, space group Monoclinic, P2(1)/c Unit cell dimensions a = 6.8212(2) Å b = 17.6275(5) Å β = 98.0530(13)º c = 17.9702(5) Å Volume 2139.44(11) Å3 Z, Calculated density 4, 1.206 Mg/m3 Absorption coefficient 2.004 mm-1 F(000) 808 Crystal size 0.52 x 0.14 x 0.07 mm Theta range for data collection 3.53 to 64.83 º Limiting indices -7<=h<=7, 0<=k<=20, 0<=l<=21 Reflections collected / unique 3556 / 3558 [R(int) = 0.0000] Completeness to theta = 64.83 98.5 % Absorption correction Empirical, Twinabs (multi-scan)




26

Max. and min. transmission 0.8659 and 0.4204 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 3558 / 0 / 354 Goodness-of-fit on F^2 1.046 Final R indices [I>2sigma(I)] R1 = 0.0322, wR2 = 0.0859 R indices (all data) R1 = 0.0350, wR2 = 0.0881 Largest diff. peak and hole 0.353 and -0.199 e-/Å-3

Crystal data and structure refinement for 1c (CCDC 824079). Identification code n0210 Empirical formula C16 H25 B10 P S Formula weight 388.49 Temperature 100(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, P2(1)/n Unit cell dimensions a = 10.5592(10 Å a = 90 º b = 14.1502(13)Å b = 93.374(7) º c = 14.2279(16)Å g = 90 º Volume 2122.2(4) Å3 Z, Calculated density 4, 1.216 Mg/m3 Absorption coefficient 0.228 mm-1 F(000) 808 Crystal size 0.23 x 0.14 x 0.14 mm Theta range for data collection 2.03 to 25.42 º Limiting indices -12<=h<=11,-16<=k<=17, -11<=l<=17 Reflections collected / unique 15217 / 3899 [R(int) = 0.0870] Completeness to theta = 25.00 99.9 %




27

Absorption correction Numerical Max. and min. transmission 0.9697 and 0.9506 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 3899 / 0 / 297 Goodness-of-fit on F^2 0.929 Final R indices [I>2sigma(I)] R1 = 0.0436, wR2 = 0.0877 R indices (all data) R1 = 0.0870, wR2 = 0.0990 Largest diff. peak and hole 0.311 and -0.440 e-/Å-3

Crystal data and structure refinement for 1d (CCDC 824080). Identification code n0572 Empirical formula C18 H29 B10 P S Formula weight 416.54 Temperature 223(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, P2(1)/n Unit cell dimensions a = 9.52690(10) Å b = 13.5196(2) Å β = 103.9870(1)º c = 18.9816(2) Å Volume 2372.34(5) Å3 Z, Calculated density 4, 1.166 Mg/m3 Absorption coefficient 0.208 mm-1 F(000) 872 Crystal size 0.34 x 0.22 x 0.15 mm Theta range for data collection 1.87 to 30.08 º Limiting indices -13<=h<=13, -19<=k<=18, -26<=l<=26 Reflections collected / unique 59573 / 6944 [R(int) = 0.0764] Completeness to theta = 30.08 99.8 %




28


Crystal data and structure refinement for 2a (CCDC 824081). Identification code n0679 Empirical formula C16 H25 B10 Cl2 P Pt S Formula weight 654.48 Temperature 100(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, P2(1)/n Unit cell dimensions a = 12.3211(2) Å b = 13.5986(2) Å β = 110.031(1)º c = 14.9381(3) Å Volume 2351.47(7) Å3 Z, Calculated density 4, 1.849 Mg/m3 Absorption coefficient 6.356 mm-1 F(000) 1256 Crystal size 0.40 x 0.27 x 0.02 mm Theta range for data collection 1.86 to 30.55 º Limiting indices -17<=h<=17, -19<=k<=19, -21<=l<=21 Reflections collected / unique 48439 / 7180 [R(int) = 0.0375] Completeness to theta = 30.55 99.6 %




29


Crystal data and structure refinement for 2c (CCDC 824082).

Identification code n0666 Empirical formula C16 H25 B10 Cl2 P Pt S Formula weight 654.48 Temperature 100(2) K Wavelength 0.71073 Å Crystal system, space group Orthorhombic, Pna2(1) Unit cell dimensions a = 14.2619(2) Å b = 11.14690(10) Å c = 15.0388(2) Å Volume 2390.81(5) Å3 Z, Calculated density 4, 1.818 Mg/m3 Absorption coefficient 6.251 mm-1 F(000) 1256 Crystal size 0.29 x 0.11 x 0.02 mm Theta range for data collection 2.27 to 30.02 º Limiting indices -20<=h<=20, -15<=k<=15, -21<=l<=20 Reflections collected / unique 61145 / 6871 [R(int) = 0.0545] Completeness to theta = 30.02 99.9 %




30

Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.8696 and 0.2652 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 6871 / 1 / 280 Goodness-of-fit on F^2 1.037 Final R indices [I>2sigma(I)] R1 = 0.0217, wR2 = 0.0394 R indices (all data) R1 = 0.0286, wR2 = 0.0413 Absolute structure parameter -0.008(4)

Crystal data and structure refinement for 2d (CCDC 824083). Identification code n0682 Empirical formula C20 H34 B10 Cl2 O0.50 P Pt S Formula weight 719.59 Temperature 100(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, P2(1)/c Unit cell dimensions a = 9.63080(10) Å b = 21.4800(3) Å β = 96.8895(6)º c = 14.1467(2) Å Volume 2905.39(7) Å3 Z, Calculated density 4, 1.645 Mg/m3 Absorption coefficient 5.153 mm-1 F(000) 1404 Crystal size 0.22 x 0.18 x 0.05 mm Theta range for data collection 1.90 to 30.02 º Limiting indices -13<=h<=13, 0<=k<=30, 0<=l<=19 Reflections collected / unique 8470 / 8470 [R(int) = 0.0000] Completeness to theta = 30.02 99.6 %




31

Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.7937 and 0.3955 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 8470 / 190 / 392 Goodness-of-fit on F^2 1.066 Final R indices [I>2sigma(I)] R1 = 0.0315, wR2 = 0.0749 R indices (all data) R1 = 0.0423, wR2 = 0.0791 Largest diff. peak and hole 1.783 and -1.992 e-/Å-3

Crystal data and structure refinement for 2f (CCDC 824084).

Identification code n0681 Empirical formula C24 H29 Cl2 P Pt S Formula weight 646.49 Temperature 100(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, P2(1)/n Unit cell dimensions a = 11.8970(19) Å b = 13.9412(13) Å β = 110.200(11)º c = 14.7305(16) Å Volume 2292.9(5) Å3 Z, Calculated density 4, 1.873 Mg/m3 Absorption coefficient 6.523 mm-1 F(000) 1264 Crystal size 0.24 x 0.22 x 0.11 mm Theta range for data collection 1.91 to 33.73 º Limiting indices -18<=h<=18, -21<=k<=21, -22<=l<=22 Reflections collected / unique 104670 / 9121 [R(int) = 0.0346] Completeness to theta = 33.73 99.4 %




32


Crystal data and structure refinement for 2g (CCDC 824085).

Identification code n0542a Empirical formula C22.50 H24 Cl3 P Pt S Formula weight 658.89 Temperature 100(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, P2(1)/c Unit cell dimensions a = 11.5740(2) Å b = 13.7870(3) Å β = 99.605(1)º c = 14.6160(3) Å Volume 2299.59(8) Å3 Z, Calculated density 4, 1.903 Mg/m3 Absorption coefficient 6.619 mm-1 F(000) 1276 Crystal size 0.363 x 0.136 x 0.022 mm Theta range for data collection 1.78 to 30.27 º Limiting indices -16<=h<=16, -19<=k<=19, -19<=l<=20 Reflections collected / unique 50657 / 6828 [R(int) = 0.0882] Completeness to theta = 30.27 99.2 %




33


Crystal data and structure refinement for 4b (CCDC 824088). Identification code n0273 Empirical formula C69 H110 B44 Cl10 F16 P4 Pt2 S4 Formula weight 2716.01 Temperature 100(2) K Wavelength 1.54178 Å Crystal system, space group Monoclinic, P2(1)/n Unit cell dimensions a = 13.1494(4) Å b = 36.1583(11) Å β = 95.836(2)º c = 23.7534(7) Å Volume 11235.3(6) Å3 Z, Calculated density 4, 1.606 Mg/m3 Absorption coefficient 8.568 mm-1 F(000) 5352 Crystal size 0.17 x 0.11 x 0.07 mm Theta range for data collection 2.23 to 65.23 º Limiting indices -15<=h<=15, -42<=k<=23, -27<=l<=27 Reflections collected / unique 82526 / 18916 [R(int) = 0.1058]




34

Completeness to theta = 65.23 98.3 % Absorption correction Numerical Max. and min. transmission 0.5854 and 0.3322 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 18916 / 0 / 1342 Goodness-of-fit on F^2 1.040 Final R indices [I>2sigma(I)] R1 = 0.0520, wR2 = 0.1212 R indices (all data) R1 = 0.0816, wR2 = 0.1354 Largest diff. peak and hole 1.751 and -1.470 e-/Å-3

Crystal data and structure refinement for 4a (CCDC 824087).

Identification code n0280 Empirical formula C32 H50 B22 F8 P2 Pt S2 Formula weight 1145.69 Temperature 100(2) K Wavelength 1.54178 Å Crystal system, space group Monoclinic, P2(1)/n Unit cell dimensions a = 13.2738(6) Å b = 18.9981(8) Å β = 105.576(3)º c = 19.6952(9) Å Volume 4784.3(4) Å3 Z, Calculated density 4, 1.591 Mg/m3 Absorption coefficient 7.433 mm-1 F(000) 2256 Crystal size 0.16 x 0.14 x 0.01 mm Theta range for data collection 3.29 to 58.24 º Limiting indices -14<=h<=14, -20<=k<=12, -20<=l<=21 Reflections collected / unique 19314 / 6621 [R(int) = 0.0918]




35

Completeness to theta = 58.24 98.4 % Absorption correction Numerical Max. and min. transmission 0.9117 and 0.5879 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 6621 / 0 / 602 Goodness-of-fit on F^2 1.019 Final R indices [I>2sigma(I)] R1 = 0.0499, wR2 = 0.1013 R indices (all data) R1 = 0.0862, wR2 = 0.1144 Largest diff. peak and hole 1.189 and -1.038 e-/Å-3

Crystal data and structure refinement for 4c (CCDC 824089). Identification code n0225 Empirical formula C33 H51 B22 Cl2 F8 P2 Pt S2 Formula weight 1229.61 Temperature 100(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, P2(1) Unit cell dimensions a = 13.5537(3) Å b = 19.4743(4) Å β = 97.8360(10)º c = 19.6358(4) Å Volume 5134.45(19) Å3 Z, Calculated density 4, 1.591 Mg/m3 Absorption coefficient 3.039 mm-1 F(000) 2420 Crystal size 0.23 x 0.21 x 0.11 mm Theta range for data collection 1.52 to 30.34 º Limiting indices -19<=h<=19, -27<=k<=27, -27<=l<=27 Reflections collected / unique 98696 / 30469 [R(int) = 0.1150] Completeness to theta = 30.34 99.4 % Absorption correction Numerical




36

Max. and min. transmission 0.7233 and 0.5378 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 30469 / 2 / 1263 Goodness-of-fit on F^2 0.976 Final R indices [I>2sigma(I)] R1 = 0.0624, wR2 = 0.1243 R indices (all data) R1 = 0.1401, wR2 = 0.1502 Absolute structure parameter 0.539(6) Largest diff. peak and hole 5.807 and -2.038 e-/Å-3

Crystal data and structure refinement for 4h (CCDC 824094). Identification code n0286 Empirical formula C40.30 H38.60 B2 Cl0.60 F8 P2 Pt S2 Formula weight 1038.95 Temperature 100(2) K Wavelength 1.54178 Å Crystal system, space group Monoclinic, P2(1) Unit cell dimensions a = 9.4556(8) Å a = 90 º b = 18.6226(10) Å b = 98.277(4) º c = 24.1172(15) Å g = 90 º Volume 4202.5(5) Å3 Z, Calculated density 4, 1.642 Mg/m3 Absorption coefficient 8.810 mm-1 F(000) 2050 Crystal size 0.50 x 0.06 x 0.03 mm Theta range for data collection 3.01 to 61.15 º Limiting indices -10<=h<=10,-21<=k<=21,-27<=l<=26 Reflections collected / unique 21417 / 21417 [R(int) = 0.0000] Completeness to theta = 61.15 98.3 %




37

Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.752559 and 0.559407 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 21417 / 318 / 1019 Goodness-of-fit on F^2 1.028 Final R indices [I>2sigma(I)] R1 = 0.0603, wR2 = 0.1366 R indices (all data) R1 = 0.0694, wR2 = 0.1419 Absolute structure parameter -0.025(12) Largest diff. peak and hole 2.343 and -2.194 e-/Å-3

Crystal data and structure refinement for 4i(CCDC 824095). Identification code n0454c Empirical formula C41 H32 B2 Cl2 F16 P2 Pt S2 Formula weight 1242.34 Temperature 100(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, P2/n Unit cell dimensions a = 10.9643(2) Å b = 14.7439(3) Å β = 96.109(1)º c = 13.6700(2) Å Volume 2197.30(7) Å3 Z, Calculated density 2, 1.878 Mg/m3 Absorption coefficient 3.583 mm-1 F(000) 1212 Crystal size 0.36 x 0.34 x 0.16 mm Theta range for data collection 2.04 to 30.01 º Limiting indices -15<=h<=15, 0<=k<=20, 0<=l<=19 Reflections collected / unique 6396 / 6396 [R(int) = 0.0000] Completeness to theta = 30.01 99.6 %




38


Crystal data and structure refinement for 4g (CCDC 824093). Identification code n0483 Empirical formula C44 H46 B2 F8 P2 Pt S2 Formula weight 1069.58 Temperature 100(2) K Wavelength 0.71073 Å Crystal system, space group Triclinic, P-1 Unit cell dimensions a = 12.6691(2) Å α = 93.780(1)º b = 19.7198(3) Å β = 107.622(1)º c = 19.9223(3) Å γ = 100.194(1)º Volume 4630.74(12) Å3 Z, Calculated density 4, 1.534 Mg/m3 Absorption coefficient 3.252 mm-1 F(000) 2128 Crystal size 0.29 x 0.21 x 0.11 mm Theta range for data collection 1.06 to 30.09 º Limiting indices -17<=h<=16, -27<=k<=27, -27<=l<=28 Reflections collected / unique 185489 / 26479 [R(int) = 0.0714] Completeness to theta = 30.09 97.3 %




39


Crystal data and structure refinement for 4d (CCDC 824090). Identification code n0512 Empirical formula C39 H64 B22 Cl6 F8 P2 Pt S2 Formula weight 1456.57 Temperature 100(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, P2(1)/c Unit cell dimensions a = 26.1737(5) Å b = 19.4713(4) Å β = 118.272(1)º c = 26.1910(5) Å Volume 11755.6(4) Å3 Z, Calculated density 8, 1.646 Mg/m3 Absorption coefficient 2.844 mm-1 F(000) 5776 Crystal size 0.40 x 0.25 x 0.11 mm Theta range for data collection 0.88 to 29.97 º Limiting indices -36<=h<=36, -27<=k<=27, -36<=l<=36 Reflections collected / unique 315108 / 34099 [R(int) = 0.1068] Completeness to theta = 29.97 99.6 %




40


Crystal data and structure refinement for 4e (CCDC 824091). Identification code n0740 Empirical formula C38 H50 B2 Cl4 F8 P2 Pt S2 Formula weight 1143.35 Temperature 273(2) K Wavelength 0.71073 Å Crystal system, space group Triclinic, P-1 Unit cell dimensions a = 12.1925(1) Å α = 84.221(1)º b = 12.9626(2) Å β = 72.108(1)º c = 15.4070(2) Å γ = 71.635(1)º Volume 2199.22(5) Å3 Z, Calculated density 2, 1.727 Mg/m3 Absorption coefficient 3.664 mm-1 F(000) 1136 Crystal size 0.48 x 0.40 x 0.31 mm Theta range for data collection 1.39 to 30.50 º Limiting indices -16<=h<=17, -18<=k<=18, 0<=l<=21 Reflections collected / unique 13225 / 13225 [R(int) = 0.0000] Completeness to theta = 30.50 98.6 %




41

Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.3982 and 0.2728 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 13225 / 0 / 466 Goodness-of-fit on F^2 1.093 Final R indices [I>2sigma(I)] R1 = 0.0209, wR2 = 0.0553 R indices (all data) R1 = 0.0232, wR2 = 0.0567 Largest diff. peak and hole 1.567 and -1.014 e-/Å-3

Crystal data and structure refinement for 4f (CCDC 824092). Identification code n0536 Empirical formula C50 H62 B2 Cl4 F8 P2 Pt S2 Formula weight 1299.57 Temperature 100(2) K Wavelength 0.71073 Å Crystal system, space group Triclinic, P-1 Unit cell dimensions a = 13.2826(3) Å α = 110.442(1)º b = 18.4796(4) Å β = 99.975(1)º c = 23.5694(5) Å γ = 91.216(1)º Volume 5318.0(2) Å3 Z, Calculated density 4, 1.623 Mg/m3 Absorption coefficient 3.041 mm-1 F(000) 2608 Crystal size 0.74 x 0.40 x 0.20 mm Theta range for data collection 0.94 to 30.02 º Limiting indices -18<=h<=18, -26<=k<=24, 0<=l<=33 Reflections collected / unique 30919 / 30919 [R(int) = 0.0000] Completeness to theta = 30.02 99.5 %




42


Crystal data structure refinement for 3i-BF4 (CCDC 824086).

Identification code n0728

Empirical formula C40 H30 B Cl F12 P2 Pt S2

Formula weight 1106.05

Temperature 100(2) K

Wavelength 0.71073 Å (MoK/α)

Crystal system, space group Monoclinic, P2(1)/n

Unit cell dimensions a = 16.4546(2)Å a = 90° b = 14.6655(2)Å b = 92.3430(10)° c = 16.6510(2)Å g = 90.00

Volume 4014.78(9) Å3

Z, Calculated density 4, 1.830 Mg/m3

Absorption coefficient 3.832 mm-1

F(000) 2160

Crystal Size 0.32 x 0.10 x 0.02 mm

Theta range for data collection 1.78 to 30.28°

Limiting indices -23<=h<=23, -20<=k<=18, -23<=l<=23

Reflections collected / unique 61801 / 11935 [R(int) = 0.0705]

Completeness to theta = 30.28 99.3 %

Absorption correction Numerical




43

Max. and min. transmission 0.9448, 0.3708

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 11935 / 0 / 532

Goodness-of-fit on F^2 0.873

Final R indices [I>2sigma(I)] R1 = 0.0274, wR2 = 0.0430

R indices (all data) R1 = 0.0512, wR2 = 0.0467

Largest diff. peak and hole 1.699 and -0.890 e-/Å-3

Figure SI-10. Crystallographically derived X-ray structure representations of 1a drawn with 40% ellipsoid probabilities.

Figure SI-11. Crystallographically derived X-ray structure representations of 1c drawn with 40% ellipsoid probabilities.




44

Figure SI-12. Crystallographically derived X-ray structure representations of 1d drawn with 40% ellipsoid probabilities.





45






46

Figure SI-16. Crystallographically derived X-ray structure representations of 2g drawn with 40% ellipsoid probabilities.

Figure SI-17. Crystallographically derived X-ray structure representations of 2f drawn with 40% ellipsoid probabilities.




47


Figure SI-19. Crystallographically derived X-ray structure representations of 4b drawn with 40% ellipsoid probabilities.




48






49

Figure SI-22. Crystallographically derived X-ray structure representations of 3i-BF4 drawn with 40% ellipsoid probabilities.

Figure SI-23. Crystallographically derived X-ray structure representations of 4e drawn with 40% ellipsoid probabilities.




50

Figure SI-24. Crystallographically derived X-ray structure representations of 4f drawn with 40% ellipsoid probabilities.

Figure SI-25. Crystallographically derived X-ray structure representations of 4g drawn with 40% ellipsoid probabilities.




51

Figure SI-26. Crystallographically derived X-ray structure representations of 4h drawn with 40% ellipsoid probabilities.

Figure SI-27. Crystallographically derived X-ray structure representations of 4i drawn with 40% ellipsoid probabilities.




52

4. Computational details.

Mulliken charges for ligands 1a-1i and NMR shielding tensors for 5a-b were obtained from DFT calculations based on the geometry-optimized structures with the ADF 2009.01 GUI. 1a, 1c and 1d were optimized from the crystallographically determined structures. Structures of 1b, 1e-1i and 5a-b were constructed in the ADF 2009.01 GUI before optimization. The optimization used basis sets containing triple-ζ functions with four polarization function (QZ4P), the local density approximation of Becke12 and Lee-Yang-Parr13 (B3LYP) with the associated default exchange and correlation corrections, and the density functional methods available in the Amsterdam Density Functional (ADF2009.01) suite on a 16-core Parallel Quantum Solutions (PQS) computational cluster (http://www.pqs-chem.com). Relativistic corrections used ZORA (zero-order relativistic approximation), and core electrons were unrestricted. Chemical shielding tensors for the 77Se nuclei were calculated from the geometry-optimized structures of 5a and 5b by the GIAO method using the ADF package (Me2Se was used as a computational reference). Becke and Lee-Yang-Parr (BLYP) generalized gradient approximation (CGA) was used for the exchange-correlation functional.

Optimized Geometry Coordinates - 5b:

ATOMS

===== X Y Z CHARGE

(Angstrom) Nucl +Core At.Mass

-------------------------- ---------------- -------

1 Se 0.9294 6.5343 19.4876 34.00 34.00 79.9165

2 B 0.9663 6.0421 24.0363 5.00 5.00 11.0093

3 H -1.1229 7.5930 24.4465 1.00 1.00 1.0078

4 B -0.1156 7.4531 23.8244 5.00 5.00 11.0093

5 B 0.8868 8.8506 23.3630 5.00 5.00 11.0093

6 B 1.4933 7.6614 24.5489 5.00 5.00 11.0093

7 H 0.7226 9.9905 23.6622 1.00 1.00 1.0078

8 H 1.7348 8.0133 25.6598 1.00 1.00 1.0078

9 H -0.8242 5.5183 22.1295 1.00 1.00 1.0078

10 H -0.8843 8.4110 21.4408 1.00 1.00 1.0078

11 H 3.6314 6.1986 24.2414 1.00 1.00 1.0078

12 H 0.7395 5.1648 24.8110 1.00 1.00 1.0078

13 H 3.3012 8.8878 23.4953 1.00 1.00 1.0078




53

14 H 1.9742 9.3003 21.0009 1.00 1.00 1.0078

15 H 3.7020 7.0577 21.3438 1.00 1.00 1.0078

16 H 2.0191 4.6290 22.0202 1.00 1.00 1.0078

17 C 1.1480 6.9151 21.4101 6.00 6.00 12.0000

18 C 2.4752 8.2181 23.2657 6.00 6.00 12.0000

19 B 1.6493 8.4941 21.8088 5.00 5.00 11.0093

20 B 2.7301 7.0927 22.0234 5.00 5.00 11.0093

21 B 1.7312 5.6955 22.4639 5.00 5.00 11.0093

22 B 0.0313 6.2350 22.5388 5.00 5.00 11.0093

23 B -0.0137 7.9661 22.1191 5.00 5.00 11.0093

24 B 2.6346 6.5745 23.7113 5.00 5.00 11.0093

25 H 1.5591 5.1974 19.5930 1.00 1.00 1.0078

TENSOR (ppm) 77Se for 5b:

***********************************

CARTESIAN AXIS REPRESENTATION

==== total shielding tensor

-----------------------------------

983.763 280.671 -145.562

280.671 805.482 616.261

-145.562 616.261 1848.623

-----------------------------------

isotropic shielding = 1212.622

***********************************

-----------------------------------

PRINCIPAL AXIS REPRESENTATION

==== Shieldings:




54

359.783 1143.503 2134.581

==== Principal Axis System:

0.452 0.892 -0.013

-0.808 0.415 0.418

0.379 -0.179 0.908

-----------------------------------

Optimized Geometry Coordinates - 5a:

ATOMS

===== X Y Z CHARGE RADIUS

(Angstrom) Nucl +Core At.Mass (Angstrom)

-------------------------- ---------------- ------- ----------

1 B 0.8226 15.8501 3.1204 5.00 5.00 11.0093 1.7920

2 Se 1.2711 17.5835 4.0831 34.00 34.00 79.9165 1.9080

3 H 0.8466 14.2026 5.2180 1.00 1.00 1.0078 1.3000

4 B 0.6589 14.3445 4.0516 5.00 5.00 11.0093 1.7920

5 B -0.7782 15.0785 3.3144 5.00 5.00 11.0093 1.7920

6 B 1.6561 13.6622 1.4239 5.00 5.00 11.0093 1.7920

7 H -1.7117 15.5202 3.9055 1.00 1.00 1.0078 1.3000

8 H 2.5076 13.0657 0.8450 1.00 1.00 1.0078 1.3000

9 H 2.1435 16.1706 0.8749 1.00 1.00 1.0078 1.3000

10 H 3.1362 14.5539 3.3533 1.00 1.00 1.0078 1.3000

11 H -1.2359 12.5289 3.7887 1.00 1.00 1.0078 1.3000

12 H -0.9186 16.6542 1.2792 1.00 1.00 1.0078 1.3000

13 H 1.5680 12.2138 3.3592 1.00 1.00 1.0078 1.3000

14 H -2.0239 14.0676 1.5114 1.00 1.00 1.0078 1.3000

15 H -0.2478 11.8576 1.1806 1.00 1.00 1.0078 1.3000




55

16 H -0.0495 14.4001 -0.4647 1.00 1.00 1.0078 1.3000

17 C 1.1101 13.1111 2.9499 6.00 6.00 12.0000 2.0000

18 C -1.0043 14.1985 1.8663 6.00 6.00 12.0000 2.0000

19 B 0.0689 12.9110 1.6245 5.00 5.00 11.0093 1.7920

20 B 0.2261 14.4101 0.6926 5.00 5.00 11.0093 1.7920

21 B 1.4426 15.4292 1.4947 5.00 5.00 11.0093 1.7920

22 B 2.0266 14.5494 2.9231 5.00 5.00 11.0093 1.7920

23 B -0.5482 13.3290 3.2472 5.00 5.00 11.0093 1.7920

24 B -0.2934 15.7528 1.7402 5.00 5.00 11.0093 1.7920

25 H 1.3283 18.3972 2.8468 1.00 1.00 1.0078 1.3000

TENSOR (ppm) 77Se for 5a:

***********************************



-----------------------------------

1738.356 76.577 -2.323

76.577 2275.671 -93.812

-2.323 -93.812 1817.041

-----------------------------------


***********************************

-----------------------------------


==== Shieldings:

1726.142 1800.706 2304.221


0.977 0.167 -0.132




56

-0.160 0.165 -0.973

-0.140 0.972 0.188

Optimized Geometry Coordinates - Me2Se reference:

ATOMS

===== X Y Z CHARGE


-------------------------- ---------------- -------

1 Se -0.1975 1.2840 0.3390 34.00 34.00 79.9165

2 C 1.4029 2.2717 -0.2817 6.00 6.00 12.0000

3 H 1.4603 3.2470 0.2144 1.00 1.00 1.0078

4 H 2.3073 1.6817 -0.0952 1.00 1.00 1.0078

5 H 1.2731 2.4151 -1.3609 1.00 1.00 1.0078

6 C 0.2858 1.1685 2.2561 6.00 6.00 12.0000

7 H 0.3747 2.1733 2.6841 1.00 1.00 1.0078

8 H -0.5345 0.6312 2.7463 1.00 1.00 1.0078

9 H 1.2181 0.6055 2.3775 1.00 1.00 1.0078

TENSOR (ppm) 77Se for Me2Se reference:

***********************************



-----------------------------------

1459.133 100.030 -199.875

100.030 1440.895 -204.030

-199.875 -204.030 1834.910

-----------------------------------


**********************************




57

-----------------------------------


==== Shieldings:

1346.724 1376.579 2011.635


0.468 -0.801 -0.375

-0.867 -0.334 -0.370

-0.171 -0.498 0.850

-----------------------------------

Molecule Isotropic Shielding Calculated Shift Experimental

Me2Se 1578.31 0 ppm (reference) 0 ppm (reference)

5a 1943.69 - 364 ppm - 280 ppm

5b 1212.62 +366 ppm +347 ppm

Table SI-1. Comparison of experimental and theoretical 77Se NMR shifts for carborane selenols.

Optimized Geometry Coordinates - Ligand 1b:

TOMS

===== X Y Z CHARGE


-------------------------- ---------------- -------

1 S 0.9201 6.5568 19.5781 16.00 16.00 31.9721

2 P 1.4008 5.7475 16.4319 15.00 15.00 30.9738

3 C 2.4867 5.7196 19.0653 6.00 6.00 12.0000

4 C 2.2066 4.8208 17.8588 6.00 6.00 12.0000

5 C 0.9938 4.3308 15.3187 6.00 6.00 12.0000

6 C 0.1188 3.3372 15.8025 6.00 6.00 12.0000

7 C -0.3174 2.3015 14.9741 6.00 6.00 12.0000

8 C 0.0928 2.2495 13.6364 6.00 6.00 12.0000




58

9 C 0.9395 3.2441 13.1382 6.00 6.00 12.0000

10 C 1.3860 4.2765 13.9700 6.00 6.00 12.0000

11 C 2.8789 6.5312 15.6414 6.00 6.00 12.0000

12 C 4.0545 5.8365 15.3022 6.00 6.00 12.0000

13 C 5.1448 6.5105 14.7469 6.00 6.00 12.0000

14 C 5.0773 7.8918 14.5222 6.00 6.00 12.0000

15 C 3.9144 8.5938 14.8521 6.00 6.00 12.0000

16 C 2.8228 7.9160 15.4078 6.00 6.00 12.0000

17 C 1.1993 6.8921 21.3447 6.00 6.00 12.0000

18 C 2.4650 8.2195 23.2407 6.00 6.00 12.0000

19 B 1.6773 8.4869 21.7682 5.00 5.00 11.0093

20 B 2.7548 7.0890 22.0064 5.00 5.00 11.0093

21 B 1.7629 5.6817 22.4395 5.00 5.00 11.0093

22 B 0.0670 6.2066 22.4663 5.00 5.00 11.0093

23 B 0.0188 7.9360 22.0322 5.00 5.00 11.0093

24 B 2.6287 6.5755 23.6971 5.00 5.00 11.0093

25 B 0.9615 6.0341 23.9918 5.00 5.00 11.0093

26 B -0.1294 7.4299 23.7353 5.00 5.00 11.0093

27 B 0.8724 8.8356 23.3014 5.00 5.00 11.0093

28 B 1.4605 7.6582 24.5041 5.00 5.00 11.0093

29 H 3.2421 6.4801 18.8291 1.00 1.00 1.0078

30 H 2.8394 5.1171 19.9115 1.00 1.00 1.0078

31 H 1.5116 4.0208 18.1490 1.00 1.00 1.0078

32 H 3.1440 4.3479 17.5309 1.00 1.00 1.0078

33 H -0.2397 3.3781 16.8331 1.00 1.00 1.0078

34 H -0.9885 1.5389 15.3724 1.00 1.00 1.0078

35 H -0.2529 1.4440 12.9867 1.00 1.00 1.0078




59

36 H 1.2581 3.2202 12.0948 1.00 1.00 1.0078

37 H 2.0448 5.0450 13.5642 1.00 1.00 1.0078

38 H 4.1160 4.7583 15.4616 1.00 1.00 1.0078

39 H 6.0495 5.9583 14.4873 1.00 1.00 1.0078

40 H 5.9312 8.4171 14.0907 1.00 1.00 1.0078

41 H 3.8554 9.6695 14.6801 1.00 1.00 1.0078

42 H 1.9157 8.4637 15.6699 1.00 1.00 1.0078

43 H 3.2821 8.8936 23.4877 1.00 1.00 1.0078

44 H 2.0142 9.2941 20.9664 1.00 1.00 1.0078

45 H 3.7562 7.0582 21.3706 1.00 1.00 1.0078

46 H 2.0747 4.6102 22.0235 1.00 1.00 1.0078

47 H -0.7711 5.4799 22.0394 1.00 1.00 1.0078

48 H -0.8389 8.3676 21.3302 1.00 1.00 1.0078

49 H 3.6167 6.2136 24.2537 1.00 1.00 1.0078

50 H 0.7250 5.1609 24.7692 1.00 1.00 1.0078

51 H -1.1540 7.5667 24.3299 1.00 1.00 1.0078

52 H 0.6872 9.9746 23.5934 1.00 1.00 1.0078

53 H 1.6737 8.0191 25.6184 1.00 1.00 1.0078

Optimized Geometry Coordinates - Ligand 1a:

ATOMS

===== X Y Z CHARGE


-------------------------- ---------------- -------

1 S 11.1882 8.7861 2.5213 16.00 16.00 31.9721

2 P 8.2416 10.4623 3.0911 15.00 15.00 30.9738

3 C 13.4479 5.1922 4.0586 6.00 6.00 12.0000

4 B 14.7393 4.9304 2.9937 5.00 5.00 11.0093




60

5 C 9.5576 7.9367 2.7157 6.00 6.00 12.0000

6 C 8.4281 8.8259 2.1935 6.00 6.00 12.0000

7 C 7.2554 10.0118 4.5895 6.00 6.00 12.0000

8 C 6.7169 8.7421 4.8579 6.00 6.00 12.0000

9 C 6.0446 8.4868 6.0588 6.00 6.00 12.0000

10 C 5.8887 9.5006 7.0083 6.00 6.00 12.0000

11 C 6.4184 10.7715 6.7539 6.00 6.00 12.0000

12 C 7.1056 11.0180 5.5640 6.00 6.00 12.0000

13 C 6.9755 11.2317 1.9804 6.00 6.00 12.0000

14 C 5.5875 11.1846 2.1881 6.00 6.00 12.0000

15 C 4.7146 11.8060 1.2885 6.00 6.00 12.0000

16 C 5.2142 12.4745 0.1659 6.00 6.00 12.0000

17 C 6.5963 12.5290 -0.0491 6.00 6.00 12.0000

18 C 7.4691 11.9235 0.8578 6.00 6.00 12.0000

19 B 13.0794 4.5510 2.5039 5.00 5.00 11.0093

20 B 12.0036 5.7313 3.3050 5.00 5.00 11.0093

21 B 13.0015 6.8237 4.2971 5.00 5.00 11.0093

22 B 14.6890 6.3383 4.0962 5.00 5.00 11.0093

23 C 15.0029 6.5154 2.4376 6.00 6.00 12.0000

24 B 14.0553 7.7247 3.1934 5.00 5.00 11.0093

25 B 12.3783 7.3649 2.6958 5.00 5.00 11.0093

26 B 12.4455 5.9335 1.5911 5.00 5.00 11.0093

27 B 14.1448 5.4412 1.4096 5.00 5.00 11.0093

28 B 13.7155 7.1720 1.5260 5.00 5.00 11.0093

29 H 13.3656 4.5190 4.9087 1.00 1.00 1.0078

30 H 15.6018 4.1371 3.1793 1.00 1.00 1.0078

31 H 9.5879 7.0045 2.1366 1.00 1.00 1.0078




61

32 H 9.4129 7.6824 3.7738 1.00 1.00 1.0078

33 H 7.4772 8.2708 2.1978 1.00 1.00 1.0078

34 H 8.6291 9.0958 1.1461 1.00 1.00 1.0078

35 H 6.8173 7.9359 4.1311 1.00 1.00 1.0078

36 H 5.6410 7.4913 6.2500 1.00 1.00 1.0078

37 H 5.3654 9.3005 7.9443 1.00 1.00 1.0078

38 H 6.3094 11.5679 7.4912 1.00 1.00 1.0078

39 H 7.5397 12.0033 5.3850 1.00 1.00 1.0078

40 H 5.1867 10.6643 3.0595 1.00 1.00 1.0078

41 H 3.6389 11.7643 1.4661 1.00 1.00 1.0078

42 H 4.5312 12.9570 -0.5344 1.00 1.00 1.0078

43 H 6.9966 13.0559 -0.9164 1.00 1.00 1.0078

44 H 8.5476 11.9922 0.7000 1.00 1.00 1.0078

45 H 12.7640 3.4092 2.4017 1.00 1.00 1.0078

46 H 10.9584 5.3543 3.7287 1.00 1.00 1.0078

47 H 12.6289 7.1927 5.3640 1.00 1.00 1.0078

48 H 15.5217 6.3929 4.9399 1.00 1.00 1.0078

49 H 16.0202 6.7773 2.1562 1.00 1.00 1.0078

50 H 14.5171 8.8010 3.3958 1.00 1.00 1.0078

51 H 11.6537 5.7870 0.7121 1.00 1.00 1.0078

52 H 14.6724 5.0087 0.4355 1.00 1.00 1.0078

53 H 13.9556 7.8996 0.6173 1.00 1.00 1.0078

Optimized Geometry Coordinates - Ligand 1d:

ATOMS

===== X Y Z CHARGE





62

-------------------------- ---------------- -------

1 S 0.0749 -0.0762 -1.6903 16.00 16.00 31.9721

2 P -2.1470 1.7961 0.3959 15.00 15.00 30.9738

3 C 3.2375 -2.0145 0.8628 6.00 6.00 12.0000

4 C 4.3638 -2.5519 -0.2690 6.00 6.00 12.0000

5 C -1.2820 -0.7215 -0.6157 6.00 6.00 12.0000

6 C -2.4574 0.2625 -0.6569 6.00 6.00 12.0000

7 C -3.4171 1.6055 1.7264 6.00 6.00 12.0000

8 C -3.7746 0.3449 2.2419 6.00 6.00 12.0000

9 C -4.6224 0.2305 3.3489 6.00 6.00 12.0000

10 C -5.1289 1.3761 3.9703 6.00 6.00 12.0000

11 C -4.7693 2.6373 3.4789 6.00 6.00 12.0000

12 C -3.9186 2.7506 2.3775 6.00 6.00 12.0000

13 C -2.8773 3.1211 -0.6708 6.00 6.00 12.0000

14 C -4.2516 3.2666 -0.9331 6.00 6.00 12.0000

15 C -4.7064 4.2637 -1.8000 6.00 6.00 12.0000

16 C -3.7948 5.1281 -2.4206 6.00 6.00 12.0000

17 C -2.4266 4.9941 -2.1664 6.00 6.00 12.0000

18 C -1.9724 3.9992 -1.2933 6.00 6.00 12.0000

19 B 2.8684 -3.4019 -0.1143 5.00 5.00 11.0093

20 B 1.6552 -2.1552 0.2341 5.00 5.00 11.0093

21 B 2.4886 -0.5813 0.3304 5.00 5.00 11.0093

22 B 4.2135 -0.8588 0.0317 5.00 5.00 11.0093

23 B 4.3955 -1.4864 -1.6158 5.00 5.00 11.0093

24 B 3.1875 -0.2374 -1.2640 5.00 5.00 11.0093

25 B 1.5829 -1.0344 -1.1497 5.00 5.00 11.0093

26 B 1.8433 -2.8021 -1.4135 5.00 5.00 11.0093




63

27 B 3.5744 -3.0611 -1.6992 5.00 5.00 11.0093

28 B 2.7840 -1.6068 -2.3493 5.00 5.00 11.0093

29 C 3.5075 -2.2466 2.3392 6.00 6.00 12.0000

30 C 5.6280 -3.2460 0.2094 6.00 6.00 12.0000

31 H -1.5892 -1.7072 -0.9903 1.00 1.00 1.0078

32 H -0.9016 -0.8404 0.4075 1.00 1.00 1.0078

33 H -3.3853 -0.2324 -0.3363 1.00 1.00 1.0078

34 H -2.6220 0.6038 -1.6893 1.00 1.00 1.0078

35 H -3.3885 -0.5676 1.7840 1.00 1.00 1.0078

36 H -4.8879 -0.7594 3.7243 1.00 1.00 1.0078

37 H -5.7945 1.2882 4.8304 1.00 1.00 1.0078

38 H -5.1536 3.5403 3.9560 1.00 1.00 1.0078

39 H -3.6470 3.7419 2.0107 1.00 1.00 1.0078

40 H -4.9699 2.6003 -0.4519 1.00 1.00 1.0078

41 H -5.7752 4.3642 -1.9949 1.00 1.00 1.0078

42 H -4.1518 5.9047 -3.0993 1.00 1.00 1.0078

43 H -1.7112 5.6652 -2.6445 1.00 1.00 1.0078

44 H -0.9046 3.8937 -1.0930 1.00 1.00 1.0078

45 H 2.8991 -4.4627 0.4250 1.00 1.00 1.0078

46 H 0.7931 -2.4272 1.0111 1.00 1.00 1.0078

47 H 2.1699 0.2124 1.1600 1.00 1.00 1.0078

48 H 5.0855 -0.3364 0.6524 1.00 1.00 1.0078

49 H 5.4483 -1.3331 -2.1523 1.00 1.00 1.0078

50 H 3.3188 0.8838 -1.6469 1.00 1.00 1.0078

51 H 1.0148 -3.5136 -1.8947 1.00 1.00 1.0078

52 H 4.0728 -3.9663 -2.2933 1.00 1.00 1.0078

53 H 2.6338 -1.4616 -3.5228 1.00 1.00 1.0078




64

54 H 5.7030 -4.2397 -0.2467 1.00 1.00 1.0078

55 H 6.5085 -2.6591 -0.0757 1.00 1.00 1.0078

56 H 5.6338 -3.3677 1.2996 1.00 1.00 1.0078

57 H 4.4368 -1.7598 2.6572 1.00 1.00 1.0078

58 H 2.6823 -1.8092 2.9139 1.00 1.00 1.0078

59 H 3.5588 -3.3157 2.5755 1.00 1.00 1.0078

Optimized Geometry Coordinates - Ligand 1c:

TOMS

===== X Y Z CHARGE


-------------------------- ---------------- -------

1 S 11.1820 8.7501 2.8185 16.00 16.00 31.9721

2 P 8.1930 10.3700 3.2943 15.00 15.00 30.9738

3 C 13.7798 5.2819 3.9584 6.00 6.00 12.0000

4 C 14.7314 5.0755 2.6544 6.00 6.00 12.0000

5 C 9.5704 7.8646 3.0478 6.00 6.00 12.0000

6 C 8.4220 8.6991 2.4726 6.00 6.00 12.0000

7 C 7.0308 10.0134 4.6868 6.00 6.00 12.0000

8 C 6.5079 8.7489 5.0045 6.00 6.00 12.0000

9 C 5.6973 8.5690 6.1319 6.00 6.00 12.0000

10 C 5.3871 9.6533 6.9572 6.00 6.00 12.0000

11 C 5.9019 10.9202 6.6535 6.00 6.00 12.0000

12 C 6.7254 11.0929 5.5398 6.00 6.00 12.0000

13 C 7.0938 11.1666 2.0349 6.00 6.00 12.0000

14 C 5.6914 11.2030 2.0977 6.00 6.00 12.0000

15 C 4.9532 11.8479 1.0990 6.00 6.00 12.0000




65

16 C 5.6040 12.4566 0.0206 6.00 6.00 12.0000

17 C 7.0020 12.4260 -0.0514 6.00 6.00 12.0000

18 C 7.7402 11.7972 0.9541 6.00 6.00 12.0000

19 B 13.0908 4.5507 2.5548 5.00 5.00 11.0093

20 B 12.2087 5.7579 3.5192 5.00 5.00 11.0093

21 B 13.3827 6.9105 4.2015 5.00 5.00 11.0093

22 B 15.0108 6.4432 3.6655 5.00 5.00 11.0093

23 B 15.0665 6.5576 1.8881 5.00 5.00 11.0093

24 B 14.1659 7.7617 2.8465 5.00 5.00 11.0093

25 B 12.4206 7.3567 2.7506 5.00 5.00 11.0093

26 B 12.2671 5.8726 1.7353 5.00 5.00 11.0093

27 B 13.9003 5.3894 1.2120 5.00 5.00 11.0093

28 B 13.4802 7.1157 1.3185 5.00 5.00 11.0093

29 H 13.9569 4.6069 4.7916 1.00 1.00 1.0078

30 H 15.4729 4.2846 2.7251 1.00 1.00 1.0078

31 H 9.6282 6.9065 2.5158 1.00 1.00 1.0078

32 H 9.4241 7.6595 4.1165 1.00 1.00 1.0078

33 H 7.4834 8.1240 2.4915 1.00 1.00 1.0078

34 H 8.6324 8.9246 1.4171 1.00 1.00 1.0078

35 H 6.7282 7.8861 4.3751 1.00 1.00 1.0078

36 H 5.3068 7.5762 6.3625 1.00 1.00 1.0078

37 H 4.7556 9.5124 7.8361 1.00 1.00 1.0078

38 H 5.6729 11.7728 7.2948 1.00 1.00 1.0078

39 H 7.1438 12.0783 5.3250 1.00 1.00 1.0078

40 H 5.1729 10.7298 2.9333 1.00 1.00 1.0078

41 H 3.8641 11.8704 1.1645 1.00 1.00 1.0078

42 H 5.0259 12.9584 -0.7572 1.00 1.00 1.0078




66

43 H 7.5194 12.9050 -0.8841 1.00 1.00 1.0078

44 H 8.8316 11.7987 0.9070 1.00 1.00 1.0078

45 H 12.8804 3.3816 2.5896 1.00 1.00 1.0078

46 H 11.2992 5.3690 4.1825 1.00 1.00 1.0078

47 H 13.2499 7.3016 5.3178 1.00 1.00 1.0078

48 H 15.9701 6.4271 4.3675 1.00 1.00 1.0078

49 H 16.1344 6.6945 1.3801 1.00 1.00 1.0078

50 H 14.5579 8.8809 2.9669 1.00 1.00 1.0078

51 H 11.3030 5.6393 1.0707 1.00 1.00 1.0078

52 H 14.1851 4.7472 0.2507 1.00 1.00 1.0078

53 H 13.3824 7.7881 0.3395 1.00 1.00 1.0078

Optimized Geometry Coordinates - Ligand 1g:

ATOMS

===== X Y Z CHARGE


-------------------------- ---------------- -------

1 S 0.9548 5.7031 19.5699 16.00 16.00 31.9721

2 P 1.5072 5.0259 16.2025 15.00 15.00 30.9738

3 C 2.2248 4.5304 18.9378 6.00 6.00 12.0000

4 C 1.9028 3.8444 17.6101 6.00 6.00 12.0000

5 C 1.6668 3.8886 14.7535 6.00 6.00 12.0000

6 C 1.5492 2.4900 14.8436 6.00 6.00 12.0000

7 C 1.5497 1.6933 13.6922 6.00 6.00 12.0000

8 C 1.6714 2.2779 12.4290 6.00 6.00 12.0000

9 C 1.7845 3.6707 12.3246 6.00 6.00 12.0000




67

10 C 1.7715 4.4651 13.4716 6.00 6.00 12.0000

11 C 3.0926 5.9853 16.1079 6.00 6.00 12.0000

12 C 4.3103 5.4537 15.6467 6.00 6.00 12.0000

13 C 5.4660 6.2391 15.6262 6.00 6.00 12.0000

14 C 5.4238 7.5671 16.0702 6.00 6.00 12.0000

15 C 4.2189 8.1075 16.5305 6.00 6.00 12.0000

16 C 3.0602 7.3223 16.5433 6.00 6.00 12.0000

17 H 2.7552 3.2039 17.3307 1.00 1.00 1.0078

18 H 1.4528 2.0055 15.8148 1.00 1.00 1.0078

19 H 1.4563 0.6101 13.7879 1.00 1.00 1.0078

20 H 6.3272 8.1794 16.0513 1.00 1.00 1.0078

21 H 4.1770 9.1427 16.8728 1.00 1.00 1.0078

22 H 1.6741 1.6562 11.5322 1.00 1.00 1.0078

23 H 1.0213 3.1973 17.7364 1.00 1.00 1.0078

24 H 2.1172 7.7465 16.8935 1.00 1.00 1.0078

25 H 1.8768 4.1405 11.3439 1.00 1.00 1.0078

26 H 1.8489 5.5495 13.3739 1.00 1.00 1.0078

27 H 4.3502 4.4234 15.2877 1.00 1.00 1.0078

28 H 6.4025 5.8149 15.2605 1.00 1.00 1.0078

29 H 3.1217 5.1598 18.8461 1.00 1.00 1.0078

30 H 2.4342 3.7788 19.7107 1.00 1.00 1.0078

31 C -0.4654 4.6426 19.8524 6.00 6.00 12.0000

32 C -0.3483 3.4820 20.6336 6.00 6.00 12.0000

33 C -1.4591 2.6845 20.9029 6.00 6.00 12.0000

34 C -2.7286 3.0405 20.4195 6.00 6.00 12.0000

35 C -2.8336 4.2124 19.6592 6.00 6.00 12.0000

36 C -1.7302 5.0260 19.3526 6.00 6.00 12.0000




68

37 H 0.6220 3.2100 21.0509 1.00 1.00 1.0078

38 H -1.3410 1.7872 21.5142 1.00 1.00 1.0078

39 H -3.8148 4.5091 19.2781 1.00 1.00 1.0078

40 C -1.9150 6.2692 18.5191 6.00 6.00 12.0000

41 H -2.9239 6.3020 18.0888 1.00 1.00 1.0078

42 H -1.7735 7.1809 19.1190 1.00 1.00 1.0078

43 H -1.1770 6.3037 17.7047 1.00 1.00 1.0078

44 C -3.9379 2.1776 20.6949 6.00 6.00 12.0000

45 H -3.9880 1.3309 19.9922 1.00 1.00 1.0078

46 H -3.9072 1.7569 21.7093 1.00 1.00 1.0078

47 H -4.8697 2.7479 20.5897 1.00 1.00 1.0078

Optimized Geometry Coordinates - Ligand 1i:

ATOMS

===== X Y Z CHARGE


-------------------------- ---------------- -------

1 S -0.4888 0.9654 2.8356 16.00 16.00 31.9721

2 P 0.0382 0.3534 -0.5743 15.00 15.00 30.9738

3 C 0.9122 -0.0137 2.1425 6.00 6.00 12.0000

4 C 0.6653 -0.7392 0.8220 6.00 6.00 12.0000

5 C 0.2959 -0.7713 -2.0186 6.00 6.00 12.0000

6 C 0.4984 -2.1589 -1.9170 6.00 6.00 12.0000

7 C 0.5652 -2.9605 -3.0633 6.00 6.00 12.0000

8 C 0.4363 -2.3898 -4.3318 6.00 6.00 12.0000

9 C 0.2312 -1.0085 -4.4474 6.00 6.00 12.0000




69

10 C 0.1504 -0.2125 -3.3045 6.00 6.00 12.0000

11 C 1.4665 1.5256 -0.7381 6.00 6.00 12.0000

12 C 2.7202 1.1731 -1.2696 6.00 6.00 12.0000

13 C 3.7500 2.1151 -1.3427 6.00 6.00 12.0000

14 C 3.5437 3.4221 -0.8828 6.00 6.00 12.0000

15 C 2.3011 3.7848 -0.3537 6.00 6.00 12.0000

16 C 1.2673 2.8435 -0.2882 6.00 6.00 12.0000

17 H 1.6113 -1.2205 0.5257 1.00 1.00 1.0078

18 H 0.6036 -2.6339 -0.9419 1.00 1.00 1.0078

19 H 0.7203 -4.0357 -2.9590 1.00 1.00 1.0078

20 H 4.3483 4.1571 -0.9447 1.00 1.00 1.0078

21 H 2.1311 4.8032 -0.0011 1.00 1.00 1.0078

22 H 0.4893 -3.0150 -5.2245 1.00 1.00 1.0078

23 H -0.0799 -1.5361 0.9651 1.00 1.00 1.0078

24 H 0.2918 3.1304 0.1096 1.00 1.00 1.0078

25 H 0.1242 -0.5515 -5.4324 1.00 1.00 1.0078

26 H -0.0267 0.8598 -3.4083 1.00 1.00 1.0078

27 H 2.8858 0.1604 -1.6429 1.00 1.00 1.0078

28 H 4.7155 1.8295 -1.7635 1.00 1.00 1.0078

29 H 1.6745 0.7696 2.0164 1.00 1.00 1.0078

30 H 1.2697 -0.7123 2.9053 1.00 1.00 1.0078

31 C -1.8347 -0.1832 2.9639 6.00 6.00 12.0000

32 C -3.1301 0.2727 2.6519 6.00 6.00 12.0000

33 C -4.2460 -0.5519 2.7926 6.00 6.00 12.0000

34 C -4.1241 -1.8655 3.2350 6.00 6.00 12.0000

35 C -2.8503 -2.3269 3.5494 6.00 6.00 12.0000

36 C -1.7305 -1.5033 3.4352 6.00 6.00 12.0000




70

37 H -4.9962 -2.5075 3.3385 1.00 1.00 1.0078

38 F -5.4718 -0.0593 2.4792 9.00 9.00 18.9984

39 F -3.3104 1.5409 2.2151 9.00 9.00 18.9984

40 F -0.5235 -2.0042 3.8104 9.00 9.00 18.9984

41 F -2.6860 -3.5992 3.9997 9.00 9.00 18.9984

Optimized Geometry Coordinates - Ligand 1h:

ATOMS

===== X Y Z CHARGE


-------------------------- ---------------- -------

1 S 1.0651 5.3101 19.7225 16.00 16.00 31.9721

2 P 1.3550 5.2557 16.2177 15.00 15.00 30.9738

3 C 2.2528 4.2935 18.7685 6.00 6.00 12.0000

4 C 1.8057 3.8429 17.3752 6.00 6.00 12.0000

5 C 1.3352 4.3677 14.5960 6.00 6.00 12.0000

6 C 1.2104 2.9735 14.4630 6.00 6.00 12.0000

7 C 1.0768 2.3812 13.2011 6.00 6.00 12.0000

8 C 1.0709 3.1702 12.0482 6.00 6.00 12.0000

9 C 1.1907 4.5614 12.1665 6.00 6.00 12.0000

10 C 1.3095 5.1519 13.4250 6.00 6.00 12.0000

11 C 2.9802 6.1489 16.1407 6.00 6.00 12.0000

12 C 4.1213 5.6603 15.4793 6.00 6.00 12.0000

13 C 5.3134 6.3896 15.4867 6.00 6.00 12.0000

14 C 5.3849 7.6169 16.1583 6.00 6.00 12.0000

15 C 4.2565 8.1148 16.8174 6.00 6.00 12.0000

16 C 3.0606 7.3875 16.8025 6.00 6.00 12.0000

17 H 2.6142 3.2404 16.9302 1.00 1.00 1.0078




71

18 H 1.2128 2.3316 15.3436 1.00 1.00 1.0078

19 H 0.9789 1.2971 13.1235 1.00 1.00 1.0078

20 H 6.3165 8.1857 16.1607 1.00 1.00 1.0078

21 H 4.3024 9.0738 17.3359 1.00 1.00 1.0078

22 H 0.9690 2.7078 11.0650 1.00 1.00 1.0078

23 H 0.9134 3.2046 17.4560 1.00 1.00 1.0078

24 H 2.1751 7.7828 17.3045 1.00 1.00 1.0078

25 H 1.1833 5.1895 11.2741 1.00 1.00 1.0078

26 H 1.3875 6.2380 13.5029 1.00 1.00 1.0078

27 H 4.0716 4.7105 14.9430 1.00 1.00 1.0078

28 H 6.1890 6.0010 14.9641 1.00 1.00 1.0078

29 H 3.1338 4.9471 18.6976 1.00 1.00 1.0078

30 H 2.5515 3.4307 19.3789 1.00 1.00 1.0078

31 C -0.2573 4.1879 20.1334 6.00 6.00 12.0000

32 C -1.4718 4.7760 20.5340 6.00 6.00 12.0000

33 C -2.5418 3.9782 20.9404 6.00 6.00 12.0000

34 C -2.4288 2.5824 20.9373 6.00 6.00 12.0000

35 C -1.2267 1.9960 20.5302 6.00 6.00 12.0000

36 C -0.1435 2.7879 20.1361 6.00 6.00 12.0000

37 H -1.5730 5.8623 20.5211 1.00 1.00 1.0078

38 H -3.4742 4.4523 21.2504 1.00 1.00 1.0078

39 H -3.2694 1.9595 21.2455 1.00 1.00 1.0078

40 H -1.1226 0.9100 20.5236 1.00 1.00 1.0078

41 H 0.7889 2.3060 19.8425 1.00 1.00 1.0078

Optimized Geometry Coordinates - Ligand 1e:

ATOMS




72

===== X Y Z CHARGE


-------------------------- ---------------- -------

1 S 9.3440 8.3887 3.5176 16.00 16.00 31.9721

2 P 7.6539 11.2796 3.3949 15.00 15.00 30.9738

3 H 5.1362 10.7933 1.7276 1.00 1.00 1.0078

4 H 6.8631 9.3276 2.1716 1.00 1.00 1.0078

5 C 7.5828 8.5004 4.0368 6.00 6.00 12.0000

6 C 6.8546 9.5860 3.2411 6.00 6.00 12.0000

7 C 7.3607 11.6105 5.1957 6.00 6.00 12.0000

8 C 6.1260 12.0108 5.7361 6.00 6.00 12.0000

9 C 5.9881 12.2212 7.1110 6.00 6.00 12.0000

10 C 7.0796 12.0284 7.9668 6.00 6.00 12.0000

11 C 8.3123 11.6297 7.4400 6.00 6.00 12.0000

12 C 8.4538 11.4304 6.0627 6.00 6.00 12.0000

13 C 6.3818 12.3488 2.5889 6.00 6.00 12.0000

14 C 6.5760 13.7434 2.6571 6.00 6.00 12.0000

15 C 5.7185 14.6218 1.9951 6.00 6.00 12.0000

16 C 4.6578 14.1256 1.2258 6.00 6.00 12.0000

17 C 4.4625 12.7455 1.1355 6.00 6.00 12.0000

18 C 5.3141 11.8646 1.8136 6.00 6.00 12.0000

19 H 5.8845 15.6974 2.0697 1.00 1.00 1.0078

20 H 5.2720 12.1711 5.0757 1.00 1.00 1.0078

21 H 3.9943 14.8109 0.6969 1.00 1.00 1.0078

22 H 7.5285 8.7204 5.1119 1.00 1.00 1.0078

23 H 5.0257 12.5380 7.5158 1.00 1.00 1.0078

24 H 7.4108 14.1416 3.2369 1.00 1.00 1.0078




73

25 H 6.9698 12.1954 9.0393 1.00 1.00 1.0078

26 H 7.0965 7.5324 3.8526 1.00 1.00 1.0078

27 H 9.1688 11.4837 8.0997 1.00 1.00 1.0078

28 H 9.4180 11.1288 5.6492 1.00 1.00 1.0078

29 H 3.6428 12.3465 0.5361 1.00 1.00 1.0078

30 H 5.8079 9.6330 3.5802 1.00 1.00 1.0078

31 C 9.8987 6.7682 4.2766 6.00 6.00 12.0000

32 H 11.8281 5.7759 4.3408 1.00 1.00 1.0078

33 H 11.5724 6.7418 2.8666 1.00 1.00 1.0078

34 C 11.3992 6.7121 3.9517 6.00 6.00 12.0000

35 H 11.9360 7.5539 4.4107 1.00 1.00 1.0078

36 H 10.1902 7.6280 6.2629 1.00 1.00 1.0078

37 H 8.0912 5.6133 3.8114 1.00 1.00 1.0078

38 C 9.1740 5.5842 3.6233 6.00 6.00 12.0000

39 H 9.3359 5.5749 2.5369 1.00 1.00 1.0078

40 H 9.5525 4.6359 4.0406 1.00 1.00 1.0078

41 C 9.6840 6.7724 5.7950 6.00 6.00 12.0000

42 H 8.6177 6.8186 6.0560 1.00 1.00 1.0078

43 H 10.0911 5.8457 6.2325 1.00 1.00 1.0078

Optimized Geometry Coordinates - Ligand 1f:

ATOMS

===== X Y Z CHARGE


-------------------------- ---------------- -------

1 C 0.0681 -0.1258 -0.4747 6.00 6.00 12.0000

2 C -0.7325 -1.2597 0.1992 6.00 6.00 12.0000

3 H 6.6165 -6.9131 -2.9526 1.00 1.00 1.0078




74

4 C -1.8688 2.1008 -0.1655 6.00 6.00 12.0000

5 C -2.0951 0.9695 -1.1920 6.00 6.00 12.0000

6 C 0.2877 1.0082 0.5536 6.00 6.00 12.0000

7 C -1.0766 1.5485 1.0392 6.00 6.00 12.0000

8 C -0.7250 0.4331 -1.6741 6.00 6.00 12.0000

9 S 1.7877 -0.6612 -0.9475 16.00 16.00 31.9721

10 H -0.1560 -1.6580 1.0496 1.00 1.00 1.0078

11 H -0.8884 -2.0921 -0.5078 1.00 1.00 1.0078

12 H 6.9992 -7.2341 -0.5082 1.00 1.00 1.0078

13 H 6.2242 -5.4918 1.1036 1.00 1.00 1.0078

14 H -2.8380 2.5064 0.1727 1.00 1.00 1.0078

15 H -2.6525 1.3601 -2.0594 1.00 1.00 1.0078

16 H 6.5638 -1.5242 -3.7796 1.00 1.00 1.0078

17 H 0.8764 1.8162 0.0895 1.00 1.00 1.0078

18 H 0.8723 0.6252 1.4066 1.00 1.00 1.0078

19 H -0.8998 2.3548 1.7702 1.00 1.00 1.0078

20 H 5.4609 -4.8825 -3.7808 1.00 1.00 1.0078

21 H -0.8796 -0.3568 -2.4280 1.00 1.00 1.0078

22 H -0.1430 1.2354 -2.1564 1.00 1.00 1.0078

23 C 1.5017 -1.9281 -2.2599 6.00 6.00 12.0000

24 C 2.5386 -3.0534 -2.1667 6.00 6.00 12.0000

25 P 4.3149 -2.4656 -2.3002 15.00 15.00 30.9738

26 H 1.5304 -1.4429 -3.2447 1.00 1.00 1.0078

27 H 0.4967 -2.3471 -2.1159 1.00 1.00 1.0078

28 C 4.6104 -2.3900 -4.1232 6.00 6.00 12.0000

29 C 3.6840 -2.7592 -5.1127 6.00 6.00 12.0000

30 C 3.9790 -2.5911 -6.4710 6.00 6.00 12.0000




75

31 C 5.2109 -2.0602 -6.8639 6.00 6.00 12.0000

32 C 6.1452 -1.6895 -5.8884 6.00 6.00 12.0000

33 C 5.8410 -1.8405 -4.5345 6.00 6.00 12.0000

34 H 2.7185 -3.1830 -4.8341 1.00 1.00 1.0078

35 H 3.2417 -2.8777 -7.2228 1.00 1.00 1.0078

36 H 5.4396 -1.9279 -7.9227 1.00 1.00 1.0078

37 H 7.1072 -1.2675 -6.1836 1.00 1.00 1.0078

38 H 2.3293 -3.8371 -2.9119 1.00 1.00 1.0078

39 H 2.4729 -3.5268 -1.1765 1.00 1.00 1.0078

40 H 5.0998 -3.4410 0.2717 1.00 1.00 1.0078

41 C 5.1788 -4.0293 -1.8108 6.00 6.00 12.0000

42 C 5.6213 -5.0141 -2.7093 6.00 6.00 12.0000

43 C 6.2747 -6.1593 -2.2413 6.00 6.00 12.0000

44 C 6.4884 -6.3402 -0.8705 6.00 6.00 12.0000

45 C 6.0531 -5.3639 0.0335 6.00 6.00 12.0000

46 C 5.4143 -4.2127 -0.4347 6.00 6.00 12.0000

47 C -1.8774 0.4079 1.7035 6.00 6.00 12.0000

48 C -2.1040 -0.7231 0.6771 6.00 6.00 12.0000

49 C -2.8932 -0.1751 -0.5312 6.00 6.00 12.0000

50 H -1.3162 2.9334 -0.6341 1.00 1.00 1.0078

51 H -2.8465 0.7887 2.0698 1.00 1.00 1.0078

52 H -1.3306 0.0202 2.5804 1.00 1.00 1.0078

53 H -2.6667 -1.5462 1.1480 1.00 1.00 1.0078

54 H -3.8811 0.1917 -0.2032 1.00 1.00 1.0078

55 H -3.0764 -0.9817 -1.2624 1.00 1.00 1.0078




76

5. References.

1. Plešek et al. Coll. Czech. Chem. Commun. 1981, 46, 687-692.

2. Zakharkin et al. Izv. Akad. Nauk SSSR, Ser. Khim. 1981, 12, 2794-2796.


4. Zakharkin et al. Zh. Obsch. Khim. 1985, 56, 2721-2728.

5. Brown et al. Angew. Chem. 2005, 117, 4279.

6. Rosen et al. Inorg. Chem. 2011, 50, 1411-1419.

7. Yoon et al. Science, 2010, 330, 66-69.

8. Cromer, D. T.; Waber, J. T. International Tables for X-ray Crystallography; The Kynoch

Press: Birmingham, England, 1974; Vol. IV.

9. Ibers, J. A.; Hamilton, W. C. Acta Crystallogr. 1964, 17, 781.

10. Creagh, D. C.; McAuley, W. J. International Tables for Crystallography; Kluwer Academic

Publishers: Boston, 1992; Vol. C.

11. Creagh, D. C.; Hubbell, J. H. International Tables for Crystallography; Kluwer Academic


12. Becke, A. D. Phys. Rev. A 1988, 38, 30982.

13. Lee et al. Phys. Rev. B 1988, 37, 785.

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76

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76

5. References.


















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