1st generation olefin metathesis catalysis containing ... · ruthenium indenylidene “1st...

S1

Supporting Information

for

Ruthenium indenylidene “1st generation” olefin metathesis

catalysis containing triisopropyl phosphite

Stefano Guidone, Fady Nahra, Alexandra M. Z. Slawin and Catherine S. J. Cazin*

Address: School of Chemistry University of St Andrews, St Andrews, UK, KY16 9ST

Fax: (+) 44 (0) 1334 463808

E-mail: [email protected]

*Corresponding author

Crystallographic data for compounds 1–3, NMR spectra of all the complexes,

spectroscopic data.

S2

Contents

1 General information .................................................................................................................... S4

2 Optimization of catalytic conditions ........................................................................................... S5

3 NMR spectra ............................................................................................................................... S6

3.1 1H NMR (CD2Cl2) of [RuCl2(Ind)(PCy3){P(OiPr)3}], 1, 293 K ....................................... S6

3.2 1H NMR (CD2Cl2) of 1, 193 K ............................................................................................ S6

3.3 31

P-{1H} NMR (CD2Cl2) of 1, 293 K .................................................................................. S7

3.4 13

C-{1H} NMR (CD2Cl2) of 1, 293 K ................................................................................. S7

3.5 1H NMR (CD2Cl2) of [RuCl2(Ind){P(OiPr)3}2] 2 in mixture with 3, 293 K. .................... S8

3.6 31P-{

1H} NMR (CD2Cl2) of 2 in mixture with 3, 293 K ..................................................... S8

3.7 13

C-{1H} NMR (CD2Cl2) of 2 in mixture with 3, 293 K ..................................................... S9

3.8 1H NMR (CD2Cl2) of Ph3P(Ind), 3, 293 K .......................................................................... S9

3.9 31

P-{1H} NMR (CD2Cl2) of 3, 293 K ................................................................................ S10

3.10 13

C-{1H} NMR (CD2Cl2) of 3, 293 K ............................................................................... S10

3.11 1H NMR (CDCl3) of 9, 293 K ........................................................................................... S11

4 trans-Species ............................................................................................................................. S11

4.1 31P-{

1H} NMR (CD2Cl2) of Ind-I

0 with 1 equiv P(OiPr)3, 15 min, 293 K ...................... S11

4.2 31P-{


0 with 1 equiv P(OiPr)3, overnight, 293 K .................. S12

4.3 31P-{


0 with 2 equiv P(OiPr)3, 15 min, 293 K ...................... S12

4.4 31P-{


0 with 2 equiv P(OiPr)3, overnight, 293 K .................. S13

5 31P EXSY experiments with complex 1 .................................................................................... S13

5.1 31P-{

1H} NMR (C7D8) of complex 1 with 5 equiv PCy3, 128 scans, 293 K ..................... S14

5.2 31P EXSY (C7D8) of complex 1 with 5 equivequiv PCy3, 128 scans, D8 = 0.6 s, 293 K . S14

5.3 31P EXSY (C7D8) of complex 1 with 5 equiv PCy3, C7D8, 128 scans, D8 = 1.2 s, 293 K S15

5.4 31P-{


5.5 31P EXSY(C7D8) of complex 1 with 5 equiv. PCy3, 128 scans, D8 = 0.6 s, 323 K .......... S16

5.6 31P EXSY (C7D8) of complex 1 with 5 equiv PCy3, 128 scans, D8 = 1.2 s, 323 K .......... S16

5.7 31P-{






5.12 31P-{


S3

6 HMRS analysis of product 3 ..................................................................................................... S20

7 Crystal data and structure refinement ....................................................................................... S21

8 References ................................................................................................................................. S21

S4

1 General information

All reactions were performed under an inert atmosphere of argon or nitrogen using standard

Schlenk line and glovebox techniques. Solvents were dispensed from a solvent purification system

from Innovative Technology. 1H,

13C-{

1H} and

31P-{

1H} NMR spectra were recorded on a Bruker

AC300 or on a Bruker Avance 400 Ultrashield spectrometer at 298 K unless otherwise stated.

Exchange spectroscopy experiments (EXSY) were carried out using a Bruker AVANCE 500 NMR

spectrometer equipped with a QNP probe tuned for 31

P observation and 1H decoupling. The

temperature was controlled by a Bruker BVT unit. The 1D selective 31

P EXSY spectra1 were

acquired with a Bruker pulse program selno which was adjusted by applying 1H waltz16 decoupling

during both acquisition and the selective 31

P excitation pulse. A standard 90° Gaussian pulse with a

duration of 10 ms was used for selective excitation. The mixing time tm (D8) ranged between 0.6

and 1.2 s. Gas chromatography analyzes were carried out using an Agilent 7890A system with a

flame ionization detector and a 5%-phenylmethylpolysiloxane column (30 m, 320 μm, film: 0.25

μm). Flash chromatography was carried out using 40–63 μm silica. Elemental analyses were

performed by the Elemental Analysis Service of the University of St Andrews or the Science Centre

of the London Metropolitan University. HMRS analysis was performed by the EPSRC National

Mass Spectrometry Service Centre at Swansea University. All reagents and commercial catalysts

were purchased and used as received unless otherwise noted.

S5

2 Optimization of catalytic conditions

Table S1: Optimization and pre-catalyst comparison in the RCM of diethyl diallylmalonate 4.a

Entry Solvent Pre-catalyst

(mol%)

T (°C) Conv. (%)b

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

CH2Cl2

CH2Cl2

toluene

toluene

toluene

toluene

toluene

toluene

toluene

toluene

toluene

toluene

toluene

toluene

toluene

1 (1)

1 (1)

1 (1)

1 (1)

1 (1)

1 (1)

1 (1)

1 (0.1)

1 (0.1)

1 (0.1)

1 (0.1)

Ind-I (0.1)

Ind-I (0.1)

Ind-I0 (0.1)

Ind-I0 (0.1)

30

50

30

60

80

100

120

70

80

100

120

80

30

30

80

4

10

2

98

> 99

> 99

95

84

94

90

82

66

98

< 1

97

aReaction conditions: substrate (0.25 mmol), pre-catalyst (0.1 to 1 mol %), solvent (0.5 mL), 14 h.

bConversions were determined by GC analysis, average of two runs.

S6

3 NMR spectra

3.1 1H NMR (CD2Cl2) of [RuCl2(Ind)(PCy3){P(OiPr)3}], 1, 293 K

1.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0 ppm

1.228

1.236

1.268

1.281

1.294

1.499

1.672

1.711

1.786

1.942

2.118

6.787

7.270

7.284

7.417

7.430

7.443

7.458

7.480

7.495

7.510

7.518

7.533

7.548

7.758

7.773

8.797

8.812

30.224

5.988

10.946

4.545

1.169

2.164

1.641

1.044

1.106

3.260

2.048

2.054

1.000

3.2 1H NMR (CD2Cl2) of 1, 193 K

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5 ppm

0.734

0.792

0.996

1.006

1.121

1.213

1.302

1.361

1.642

1.704

1.807

2.026

2.287

2.565

2.589

3.119

3.533

3.555

4.639

4.784

6.655

7.256

7.271

7.407

7.422

7.436

7.449

7.464

7.509

7.523

7.679

7.694

8.690

8.704

3.727

58.134

1.115

0.931

0.966

0.942

1.004

0.973

0.975

1.012

3.757

0.793

0.390

2.062

1.007

S7

3.3 31

P-{1H} NMR (CD2Cl2) of 1, 293 K

-150-100-50150 100 50 0 ppm

33.623

47.076

47.298

122.135

122.357

The phosphorous nuclei exhibit different relaxation times. Traces of impurities at 33.5 ppm with no

influence on the elemental analysis.

3.4 13

C-{1H} NMR (CD2Cl2) of 1, 293 K

300 250 200 150 100 50 ppm

24.487

24.517

26.891

28.061

28.142

28.411

28.489

30.120

30.578

35.338

71.492

118.447

126.983

129.631

129.699

130.188

130.341

130.683

135.108

136.502

140.559

141.232

141.270

141.344

141.380

147.821

206.790

290.146

290.243

290.340

290.442

120125130135140145 ppm

118.447

126.983

129.631

129.699

130.188

130.341

130.683

135.108

136.502

140.559

141.232

141.270

141.344

141.380

147.821

14161820222426283032343638 ppm

24.354

24.487

24.517

26.891

28.061

28.142

28.411

28.489

30.120

30.578

35.338

S8

3.5 1H NMR (CD2Cl2) of [RuCl2(Ind){P(OiPr)3}2] 2 in mixture with 3, 293 K.

1.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5 ppm

1.111

1.132

1.293

1.313

4.492

4.510

4.526

4.542

4.561

6.693

6.709

6.747

6.770

6.856

6.882

6.926

6.952

6.976

7.033

7.058

7.081

7.172

7.242

7.265

7.301

7.337

7.393

7.419

7.447

7.473

7.507

7.531

7.560

7.567

7.582

7.592

7.668

7.693

19.664

20.454

6.566

0.488

0.255

0.299

0.341

1.249

10.695

4.092

0.195

1.000

3.6 31

P-{1H} NMR (CD2Cl2) of 2 in mixture with 3, 293 K

-150-100-50150 100 50 0 ppm

10.916

123.001

Traces of impurities detected at -3 ppm.

S9

3.7 13

C-{1H} NMR (CD2Cl2) of 2 in mixture with 3, 293 K

406080100120140160180200220240260280300 ppm

14.203

23.972

24.418

53.101

53.461

53.822

54.182

54.542

71.451

118.225

118.453

118.707

118.944

119.342

123.737

127.055

128.636

128.815

128.908

129.097

129.504

129.603

129.663

130.004

130.217

130.326

131.214

133.304

133.920

134.153

134.287

134.833

136.770

140.264

140.592

140.705

150.199

291.088

120125130135140145150155 ppm118.944

119.342

123.737

127.055

128.636

128.815

128.908

129.097

129.504

129.603

129.663

130.004

130.217

130.326

131.214

133.304

133.920

134.153

134.287

134.833

136.770

140.264

140.592

140.705

150.199

3.8 1H NMR (CD2Cl2) of Ph3P(Ind), 3, 293 K

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

6.721

6.734

6.749

6.752

6.769

6.786

6.789

6.883

6.903

6.955

6.957

6.972

6.974

6.977

6.992

6.994

7.059

7.061

7.077

7.095

7.301

7.321

7.339

7.566

1.012

0.980

0.992

1.006

1.011

2.073

5.979

2.104

8.936

1.000

6.76.86.97.07.17.27.37.47.57.67.77.87.98.08.1 ppm

6.749

6.752

6.769

6.786

6.789

6.883

6.903

6.955

6.957

6.972

6.974

6.977

6.992

6.994

7.059

7.061

7.077

7.095

7.301

7.321

7.339

7.566

7.691

7.954

7.956

7.958

7.974

7.976

7.978

1.012

0.980

0.992

1.006

1.011

2.073

5.979

2.104

8.936

1.000

S10

3.9 31

P-{1H} NMR (CD2Cl2) of 3, 293 K

-40-30-20-1060 50 40 30 20 10 0 ppm

10.930

3.10 13

C-{1H} NMR (CD2Cl2) of 3, 293 K

556065707580859095100105110115120125130135140145 ppm

53.681

53.839

54.038

54.200

54.400

54.560

67.767

69.379

118.252

118.483

118.735

119.390

121.108

121.314

123.767

125.042

126.234

127.099

127.744

127.961

128.665

129.521

129.684

133.323

133.357

134.168

134.305

134.898

135.084

137.093

137.269

140.506

120125130135140 ppm

118.252

118.483

118.735

119.390

121.108

121.314

123.767

125.042

126.234

127.099

127.744

127.961

128.665

129.521

129.684

133.323

133.357

134.168

134.305

134.898

135.084

137.093

137.269

140.506

S11

3.11 1H NMR (CDCl3) of 9, 293 K

1.52.02.53.03.54.04.55.05.56.06.57.0 ppm

1.248

1.265

1.283

1.724

1.727

2.919

2.921

2.979

2.984

2.989

4.183

4.200

4.218

4.236

5.203

5.207

6.601

3.050

2.035

2.051

4.344

1.000

4 trans-Species

In a glovebox, an NMR tube was charged with Ind-I0 (20 mg, 0.023 mmol) and triisopropyl

phosphite (5 μL, 0.026 mmol; 10 μL, 0.048 mmol) and dichloromethane (0.5 mL). The reaction was

monitored by 31

P-{1H} NMR spectroscopy.

4.1 31

P-{1H} NMR (CD2Cl2) of Ind-I

0 with 1 equiv P(OiPr)3, 15 min, 293 K

-150-100-50150 100 50 0 ppm

-5.627

-3.446

4.144

19.341

22.377

27.154

28.096

108.076

110.602

111.108

122.861

124.631

139.822

253035404550556065707580859095100105110115 ppm

19.341

22.377

27.154

28.096

108.076

110.602

111.108

2JPP 491 Hz

PPh3

S12

4.2 31


0 with 1 equiv P(OiPr)3, overnight, 293 K

-10130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

-5.619

-3.443

10.767

27.159

28.093

47.927

48.189

118.508

122.867

123.887

124.149

4.3 31


0 with 2 equiv P(OiPr)3, 15 min, 293 K

-150-100-50150 100 50 0 ppm

-5.620

-3.446

27.152

110.586

111.097

122.862

139.824

PPh3

P(OiPr)3

PPh3

2JPP 43 Hz

S13

4.4 31


0 with 2 equiv P(OiPr)3, overnight, 293 K

-150-100-50150 100 50 0 ppm

-5.620

-3.438

4.138

10.775

27.142

117.886

122.883

132.208

139.844

5 31

P EXSY experiments with complex 1

General Procedure. In a glovebox, a NMR tube was charged with complex 1 (5.2 mg, 0.006

mmol, 1 equiv), PCy3 (8.3 mg, 0.03 mmol, 5 equiv) and dissolved in toluene-d8 (0.5 mL). 31

P-{1H}

NMR spectra were recorded before and after any 31

P EXSY experiment in order to monitor the

composition of the solution. 31

P EXSY experiments were run at 293 K, 323 K, 353 K and back to

293 K with the same sample in sequence (see 5.1-5.12).

PPh3

P(OiPr)3

S14

5.1 31

P-{1H} NMR (C7D8) of complex 1 with 5 equiv PCy3, 128 scans, 293 K

-40-20180 160 140 120 100 80 60 40 20 0 ppm

9.731

33.603

46.936

47.109

122.257

122.435

5.2 31

P EXSY (C7D8) of complex 1 with 5 equiv PCy3, 128 scans, D8 = 0.6 s, 293 K

-20-10180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

9.712

No exchange observed with complex 1.

PCy3

S15

5.3 31

P EXSY (C7D8) of complex 1 with 5 equiv PCy3, C7D8, 128 scans, D8 = 1.2 s, 293 K

-20200 180 160 140 120 100 80 60 40 20 0 ppm

9.709


5.4 31


-30-20-10170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

10.333

31.443

33.525

47.011

121.570

121.746

20406080100120 ppm

10.333

31.443

33.525

47.011

121.570

121.746

Reference spectrum of the NMR sample at 323 K. Some decomposition observed at 33.5 ppm.

S16

5.5 31

P EXSY(C7D8) of complex 1 with 5 equiv PCy3, 128 scans, D8 = 0.6 s, 323 K

-20-10150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

10.321


5.6 31


-10140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

10.320

49.916

No exchange observed with complex 1. Peak at 49.9 ppm might represent a transient species

exchanging phosphine under such conditions.

S17

5.7 31


160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

10.933

30.926

33.418

47.094

47.268

120.877

121.052

120 100 80 60 40 20 ppm

10.933

30.926

33.418

47.094

47.268

120.877

121.052

Reference spectrum of the NMR sample at 353 K. Some decomposition observed at 33.4 ppm.

5.8 31


-20-10170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

10.919

30.935


exchanging phosphine under such conditions, different from the previous one at 323 K.

S18

5.9 31


-40-30-20-10160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

10.916

30.938



5.10 31


-100-50150 100 50 0 ppm

10.916

30.943



S19

5.11 31


-20200 180 160 140 120 100 80 60 40 20 0 ppm

10.912

30.944

181.704

No exchange observed with complex 1. Peaks at 30.9 and 181.7 ppm might represent transient

species exchanging phosphine under such conditions, different from the previous ones at 323 K.

5.12 31


130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

9.761

31.919

33.487

46.939

47.119

122.209

122.387

124.883

120 100 80 60 40 20 ppm

9.761

31.919

33.487

46.939

47.119

122.209

122.387

124.883

Final spectrum of the NMR sample back at 293 K. Some decomposition observed at 33.4 and 124.9

ppm.

S20

6 HRMS analysis of product 3

S21

7 Crystal data and structure refinement

CCDC/889638 1 CCDC/889639 2 CCDC/889640 3

Identification number sgcc1 sgcc2 sgcc6

Empirical formula C45 H71 Cl2 O3 P2 Ru C33 H52 Cl2 O6 P2 Ru C33.25 H25.50 Cl0.50 P

Formula weight 893.93 778.66 473.73

Temperature (K) 125(2) 93(2) 93(2)

Wavelength (Å) 0.71073 0.71073 0.71073

Crystal system Orthorhombic Orthorhombic Orthorhombic

Space group Pbca Pbca P2(1)2(1)2

Unit cell dimensions a,b,c

(Å); α,β,γ (°)

13.703(2), 16.085(3),

41.003(7); 90, 90, 90

13.067(2), 15.910(2),

37.178(6); 90, 90, 90

18.848(4), 25.980(5),

10.209(2); 90, 90, 90

Volume (Å3) 9038(3) 7729(2) 4999.1(18)

Z 8 8 8

Density (calcd) (Mg/m3) 1.314 1.338 1.259

Absorption coeff. (mm-1

) 0.573 0.665 0.184

F(000) 3784 3248 1988

Crystal size (mm3) 0.18 x 0.14 x 0.03 0.20 x 0.20 x 0.02 0.05 x 0.05 x 0.05

Theta range for data

collection (°)

0.99 to 25.45 2.30 to 25.38 2.14 to 25.38

Index ranges -16<=h<=16, -19<=k<=17,

-43<=l<=49

-12<=h<=15, -18<=k<=17,

-44<=l<=41

-20<=h<=22, -31<=k<=31,

-12<=l<=12

Reflections collected 67079 35597 50745

Independent reflections 8344 [R(int) = 0.1184] 6784 [R(int) = 0.0687] 9203 [R(int) = 0.1646]

Completeness to theta =

25.00°

99.7 % 95.9 % 99.9 %

Absorption correction Semi-empirical from

equivalents

Multiscan Multiscan

Max. and min. transmission 1.000 and 0.548 1.000 and 0.791 1.000 and 0.558

Refinement method Full-matrix least-squares on

F2

Full-matrix least-squares on

F2

Full-matrix least-squares on

F2

Data / restraints /

parameters

8344 / 0 / 485 6784 / 0 / 397 9203 / 0 / 630

Goodness-of-fit on F2 1.270 1.071 0.944

Final R indices

[I>2sigma(I)]

R1 = 0.0730, wR2 = 0.1980 R1 = 0.0433, wR2 = 0.0891 R1 = 0.0796, wR2 = 0.2041

R indices (all data) R1 = 0.0992, wR2 = 0.2295 R1 = 0.0642, wR2 = 0.0979 R1 = 0.1053, wR2 = 0.2199

Largest diff. peak and hole

(eÅ-3)

1.119 and -1.678 0.528 and -0.547 0.197 and -0.243

8 References

1. Bauer, C. J.; Freeman, R.; Frenkiel, T.; Keeler, J.; Shaka A. J. J. Magn. Reson. 1984, 58, 442–

457.

1st generation olefin metathesis catalysis containing ... · ruthenium indenylidene “1st...

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