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Electronic Supplementary Informationfor
Synthesis and catalytic activity of palladium complexes bearing N-heterocyclic carbenes (NHCs) and 1,4,7-triaza-9-phosphatricyclo[5.3.2.1]tridecane (CAP)
ligands
Thomas Scattolin,a Vladislav A. Voloshkin,a Ekaterina Martynova,a Sofie M. P. Vanden Broeck,a Marek Beliš,a
Catherine S. J. Cazina and Steven P. Nolana*
NMR spectra
Figure S1: 1H NMR spectrum of 2a in CDCl3 at 298 K
S1
Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2021
Figure S2: 31P{1H} NMR spectrum of 2a in CDCl3 at 298 K
S2
Figure S3: 13C{1H} DEPT Q NMR spectrum of 2a in CDCl3 at 298 K
Figure S4: 1H NMR spectrum of 2b in CDCl3 at 298 K
S3
Figure S5: 31P{1H} NMR spectrum of 2b in CDCl3 at 298 K
Figure S6: 13C{1H} DEPT Q NMR spectrum of 2b in CDCl3 at 298 K
S4
Figure S7: 1H NMR spectrum of 2c in CDCl3 at 298 K
S5
Figure S8: 31P{1H} NMR spectrum of 2c in CDCl3 at 298 K
Figure S9: 13C{1H} DEPT Q NMR of 2c in CDCl3 at 298 K
S6
Figure S10: 1H NMR spectrum of 2d in CDCl3 at 298 K
Figure S11: 31P{1H} NMR spectrum of 2b in CDCl3 at 298 K
S7
Figure S12: 13C{1H} DEPT Q NMR spectrum of 2d in CDCl3 at 298 K
S8
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.51H (ppm)
24.0
0
12.0
6
2.91
2.96
2.98
2.99
3.02
3.05
3.84
5.32
5.32
CD
2Cl2
5.32
5.32
5.33
Figure S13: 1H NMR spectrum of 4 in CD2Cl2 at 298 K
-220-180-140-100-70-40-1002040608011014031P (ppm)
41.7
3
Figure S14: 31P{1H} NMR spectrum of 4 in CDCl3 at 298 K
S9
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.51H (ppm)
12.9
3
6.30
2.10
1.03
2.00
2.82
2.84
2.85
2.86
2.87
2.88
2.88
2.89
2.92
2.93
2.94
2.95
2.96
2.97
2.98
2.99
3.00
3.01
3.02
3.92
3.94
7.26
Chl
orof
orm
-d7.
327.
327.
337.
347.
347.
357.
367.
367.
717.
717.
727.
737.
747.
757.
767.
777.
778.
868.
878.
888.
89
Figure S15: 1H NMR spectrum of 5 in CDCl3 at 298 K
-220-180-140-100-70-40-1002040608011014031P (ppm)
31.6
2
S10
Figure S16: 31P{1H} NMR spectrum of 5 in CDCl3 at 298 K
010203040506070809010011012013014015016017018019020013C (ppm)
49.7
849
.88
50.7
1
76.7
477
.16
77.5
8
124.
60
138.
05
150.
70
Figure S17: 13C{1H} DEPT Q NMR spectrum of 5 in CDCl3 at 298 K
-1.00.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.51H (ppm)
12.7
9
6.00
2.86
2.88
2.89
2.91
2.91
2.92
2.93
2.93
2.95
2.96
2.97
2.98
3.00
3.01
3.01
3.02
3.03
3.04
3.05
3.06
3.07
3.08
3.49
3.50
7.26
Chl
orof
orm
-d
S11
NP
NN
Se
Figure S18: 1H NMR spectrum of CAP=Se in CDCl3 at 298 K
-100-90-80-70-60-50-40-30-20-10010203040506070809010011031P (ppm)
29.5
231
.60
33.6
8
Figure S19: 31P{1H} NMR spectrum of CAP=Se in CDCl3 at 298 K
010203040506070809010011012013014015016017018019020021022013C (ppm)
50.8
450
.85
55.8
956
.17
77.1
6 Ch
loro
form
-d
S12
NP
NN
Se
Figure S20: 13C{1H} DEPT Q NMR spectrum of CAP=Se in CDCl3 at 298 K
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.51H (ppm)
4.00
3.04
3.94
3.95
3.04
3.06
3.08
3.77
3.85
3.86
3.88
6.84
6.85
6.86
6.87
6.88
6.88
6.89
6.91
6.92
7.26
Chl
orof
orm
-d
Figure S21: 1H NMR spectrum of 6a in CDCl3 at 298 K
S13
N
O
O
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.51H (ppm)
2.66
3.01
3.36
1.87
1.81
2.15
3.26
3.82
6.71
6.72
6.74
6.74
6.77
6.78
6.78
6.79
6.80
6.81
6.87
6.88
6.89
6.90
6.91
6.92
7.07
7.08
7.09
7.10
7.11
7.12
7.17
7.20
7.20
7.23
7.26
Figure S22: 1H NMR spectrum of 6b in CDCl3 at 298 K
-1.00.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.51H (ppm)
4.00
4.03
4.08
1.96
1.06
2.01
3.54
3.55
3.56
4.05
4.06
4.07
7.26
7.44
7.44
7.46
7.46
7.46
7.48
7.48
7.48
7.48
7.49
7.50
7.50
7.52
7.52
8.01
8.01
8.01
8.03
8.03
8.34
8.53
8.54
8.54
8.56
8.56
Figure S23: 1H NMR spectrum of 6c in CDCl3 at 298 K
S14
N
O
N
O
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.51H (ppm)
3.00
1.81
2.64
3.93
3.28
3.35
3.42
6.83
6.86
7.16
7.16
7.16
7.17
7.18
7.18
7.18
7.19
7.19
7.19
7.20
7.21
7.26
7.36
7.36
7.38
7.38
7.39
7.39
7.40
7.41
7.42
7.42
7.44
7.44
Figure S24: 1H NMR spectrum of 6d in CDCl3 at 298 K
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.51H (ppm)
4.17
4.15
2.06
2.00
3.23
3.24
3.25
3.26
3.86
3.87
3.88
3.89
6.93
6.96
7.26
7.49
7.52
S15
N
CF3
N
O
F3C
Figure S25: 1H NMR spectrum of 6e in CDCl3 at 298 K
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.51H (ppm)
4.00
3.94
0.98
0.97
1.02
1.90
0.95
3.25
3.27
3.29
3.89
3.90
3.92
7.00
7.01
7.26
7.28
7.30
7.31
7.33
7.45
7.45
7.48
7.49
7.97
8.00
8.70
8.71
8.72
8.72
Figure S26: 1H NMR spectrum of 6f in CDCl3 at 298 K
S16
N
N
O
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.51H (ppm)
3.01
4.06
1.04
2.01
1.04
1.00
3.34
7.05
7.07
7.08
7.08
7.08
7.10
7.10
7.11
7.12
7.15
7.15
7.16
7.16
7.21
7.21
7.22
7.22
7.26
7.31
7.31
7.33
7.34
7.36
8.12
8.13
8.14
8.14
8.30
8.31
Figure S27: 1H NMR spectrum of 6g in CDCl3 at 298 K
Calorimetry results
Figure S28: Calorimetric output of the reaction of 3a and CAP in CH2Cl2 at 30°C (repetition 1).
S17
N
N
Figure S29: Calorimetric output of the reaction of 3a and CAP in CH2Cl2 at 30°C (repetition 2).
Figure S30: Calorimetric output of the reaction of 3a and CAP in CH2Cl2 at 30°C (repetition 3).
S18
Figure S31: Calorimetric output of the reaction of 3a and PPh3 in CH2Cl2 at 30°C (repetition 1).
Figure S32: Calorimetric output of the reaction of 3a and PPh3 in CH2Cl2 at 30°C (repetition 2).
S19
Figure S33: Calorimetric output of the reaction of 3a and PPh3 in CH2Cl2 at 30°C (repetition 3).
S20
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