1st generation olefin metathesis catalysis containing ... · ruthenium indenylidene “1st...
TRANSCRIPT
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-{
1H} NMR (CD2Cl2) of Ind-I
0 with 1 equiv P(OiPr)3, overnight, 293 K .................. S12
4.3 31P-{
1H} NMR (CD2Cl2) of Ind-I
0 with 2 equiv P(OiPr)3, 15 min, 293 K ...................... S12
4.4 31P-{
1H} NMR (CD2Cl2) of Ind-I
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-{
1H} NMR (C7D8) of complex 1 with 5 equiv PCy3, 128 scans, 323 K ..................... S15
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-{
1H} NMR (C7D8) of complex 1 with 5 equiv PCy3, 128 scans, 353 K ..................... S17
5.8 31P EXSY (C7D8) of complex 1 with 5 equiv PCy3, 128 scans, D8 = 0.6 s, 353 K .......... S17
5.9 31P EXSY (C7D8) of complex 1 with 5 equiv PCy3, 128 scans, D8 = 1.2 s, 353 K .......... S18
5.10 31P EXSY (C7D8) of complex 1 with 5 equiv PCy3, 512 scans, D8 = 0.6 s, 353 K .......... S18
5.11 31P EXSY (C7D8) of complex 1 with 5 equiv PCy3, 512 scans, D8 = 1.2 s, 353 K .......... S19
5.12 31P-{
1H} NMR (C7D8) of complex 1 with 5 equiv PCy3, 128 scans, 293 K ..................... S19
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
P-{1H} NMR (CD2Cl2) of Ind-I
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
P-{1H} NMR (CD2Cl2) of Ind-I
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
P-{1H} NMR (CD2Cl2) of Ind-I
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
No exchange observed with complex 1.
5.4 31
P-{1H} NMR (C7D8) of complex 1 with 5 equiv PCy3, 128 scans, 323 K
-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
No exchange observed with complex 1.
5.6 31
P EXSY (C7D8) of complex 1 with 5 equiv PCy3, 128 scans, D8 = 1.2 s, 323 K
-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
P-{1H} NMR (C7D8) of complex 1 with 5 equiv PCy3, 128 scans, 353 K
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
P EXSY (C7D8) of complex 1 with 5 equiv PCy3, 128 scans, D8 = 0.6 s, 353 K
-20-10170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
10.919
30.935
No exchange observed with complex 1. Peak at 30.9 ppm might represent a transient species
exchanging phosphine under such conditions, different from the previous one at 323 K.
S18
5.9 31
P EXSY (C7D8) of complex 1 with 5 equiv PCy3, 128 scans, D8 = 1.2 s, 353 K
-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
No exchange observed with complex 1. Peak at 30.9 ppm might represent a transient species
exchanging phosphine under such conditions, different from the previous one at 323 K.
5.10 31
P EXSY (C7D8) of complex 1 with 5 equiv PCy3, 512 scans, D8 = 0.6 s, 353 K
-100-50150 100 50 0 ppm
10.916
30.943
No exchange observed with complex 1. Peak at 30.9 ppm might represent a transient species
exchanging phosphine under such conditions, different from the previous one at 323 K.
S19
5.11 31
P EXSY (C7D8) of complex 1 with 5 equiv PCy3, 512 scans, D8 = 1.2 s, 353 K
-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
P-{1H} NMR (C7D8) of complex 1 with 5 equiv PCy3, 128 scans, 293 K
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.