The synthesis of some “reverse pyridine” bis(phosphinite) pincer complexes of nickel and rhodium is reported. N-Functionalization of a POCOP ligand with a borane Lewis acid was found to permit cyclometalation with metal precursors, which reacted with the free base ligand in an undesired manner. Convenient removal of the coordinated Lewis acid was accomplished using polymer-supported 4-dimethylaminopyridine. The effects of borane Lewis acid coordination on the physical and spectroscopic properties of the pincer complexes were also assessed

Grubbs, Robert H.

Swisher, Nicholas A.

English

Caltech Authors - Main

 S1 
Supporting Information 
 
 
Synthesis and Characterization of 3,5-Bis(di-tert-
butylphosphinito)pyridine Pincer Complexes 
 
Nicholas A. Swisher and Robert H. Grubbs 
 
 
Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of 
Technology, Pasadena, California 91125, United States 
 
 
Table of Contents: 
 
1. NMR Spectra                     S2-S25 
 
2. Infrared Spectra                                                   S26-S27 
 
3. Cyclic Voltammetry Data                 S28-S29 
         
4. X-Ray Crystallographic Information               S30-S31 
  
5. References                   S32 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 S2 
 
 
 
Nuclear Magnetic Resonance Spectra 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S1. 1H NMR (400 MHz, C6D6) spectrum of 3,5-bis(di-tert-butylphosphinito)pyridine, 1. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-2-101234567891011121314
f1	(ppm)
3
6
.0
0
1.
3
0
1.
8
7
0
.9
9
1.
0
2
7.
12
7.
74
7.
75
7.
76
8
.5
4
8
.5
5
8
.5
5
N
OP(tBu)2(tBu)2PO
 S3 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S2. 1H NMR (400 MHz, CD2Cl2) spectrum of 3,5-bis(di-tert-butylphosphinito)pyridine, 
1. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-2-101234567891011121314
f1	(ppm)
3
6
.0
0
0
.9
1
1.
3
2
1.
15
1.
18
5.
3
2
7.
3
6
7.
3
6
7.
3
7
8
.0
6
8
.0
7
8
.0
7
N
OP(tBu)2(tBu)2PO
 S4 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S3. 31P{1H} NMR (162 MHz, C6D6) spectrum of 3,5-bis(di-tert-
butylphosphinito)pyridine, 1.  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-40-30-20-100102030405060708090100110120130140150160170180190
f1	(ppm)
15
7.
6
5
N
OP(tBu)2(tBu)2PO
 S5 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S4. 13C{1H} NMR (101 MHz, C6D6) of 3,5-bis(di-tert-butylphosphinito)pyridine, 1.  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-100102030405060708090100110120130140150160170180190200210
f1	(ppm)
26
.8
8
27
.0
3
3
5.
27
3
5.
54
11
4
.1
1
11
4
.2
5
11
4
.3
9
13
4
.6
1
13
4
.7
1
15
6
.8
0
15
6
.8
9
N
OP(tBu)2(tBu)2PO
 S6 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S5. 1H NMR (400 MHz, C6D6) spectrum of N-tris(pentafluorophenyl)borane-3,5-bis(di-
tert-butylphosphinito)pyridine, 2. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-101234567891011121314
f1	(ppm)
3
6
.0
0
1.
0
0
2.
0
5
0
.8
7
0
.9
0
7.
16
7.
6
2
8
.6
9
N
OP(tBu)2(tBu)2PO
B(C6F5)3
 S7 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S6.  31P{1H} NMR (162 MHz, C6D6) spectrum of N-tris(pentafluorophenyl)borane-3,5-
bis(di-tert-butylphosphinito)pyridine, 2. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-40-30-20-100102030405060708090100110120130140150160170180190
f1	(ppm)
17
0
.6
4
N
OP(tBu)2(tBu)2PO
B(C6F5)3
 S8 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S7. 19F{1H} NMR (376 MHz, C6D6) spectrum of N-tris(pentafluorophenyl)borane-3,5-
bis(di-tert-butylphosphinito)pyridine, 2. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100102030
f1	(ppm)
-1
6
3
.0
8
-1
6
3
.0
3
-1
6
2.
9
8
-1
55
.8
0
-1
55
.7
5
-1
55
.6
9
-1
3
1.
4
8
N
OP(tBu)2(tBu)2PO
B(C6F5)3
 S9 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S8. 13C{1H} NMR (101 MHz, C6D6) of N-tris(pentafluorophenyl)borane-3,5-bis(di-tert-
butylphosphinito)pyridine, 2. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-100102030405060708090100110120130140150160170180190200210
f1	(ppm)
26
.6
8
26
.8
4
3
5.
8
1
3
6
.0
9
12
1.
54
12
1.
6
2
12
1.
71
12
7.
8
2
12
8
.0
6
12
8
.3
0
13
1.
8
9
13
2.
0
8
13
6
.5
3
13
9
.0
6
14
1.
8
8
14
7.
10
14
9
.5
0
15
8
.7
3
15
8
.8
2
N
OP(tBu)2(tBu)2PO
B(C6F5)3
 S10 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S9. 1H NMR (400 MHz, CD2Cl2) spectrum of (PyPOCOP)Rh(CO), 3.  Contamination by 
small amounts of silicone grease and pentane is present. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
N
OO
(tBu)2P P(tBu)2Rh
CO
-2-101234567891011121314
f1	(ppm)
3
6
.0
0
1.
21
0
.0
8
0
.8
8
1.
3
1
1.
3
3
1.
3
5
5.
3
2
7.
8
5
 S11 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S10. 31P{1H} NMR (162 MHz, CD2Cl2) spectrum of (PyPOCOP)Rh(CO), 3. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-50-30-101030507090110130150170190210230250270290
f1	(ppm)
21
9
.8
5
22
0
.8
1
N
OO
(tBu)2P P(tBu)2Rh
CO
 S12 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S11.  13C{1H} NMR (101 MHz, CD2Cl2) of (PyPOCOP)Rh(CO), 3. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-100102030405060708090100110120130140150160170180190200210
f1	(ppm)
28
.4
1
28
.4
5
28
.4
9
3
9
.9
3
3
9
.9
5
4
0
.0
1
4
0
.0
3
4
0
.0
9
4
0
.1
1
53
.3
0
53
.5
7
53
.8
4
54
.1
1
54
.3
8
12
5.
9
2
12
5.
9
8
12
6
.0
4
15
3
.8
9
15
3
.9
8
15
4
.1
5
16
5.
9
2
16
6
.0
1
16
6
.0
9
19
9
.8
5
19
9
.9
5
20
0
.0
4
20
0
.4
4
20
0
.5
4
20
0
.6
3
N
OO
(tBu)2P P(tBu)2Rh
CO
 S13 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S12. 1H NMR (400 MHz, CD2Cl2) spectrum of (BCF-PyPOCOP)Rh(CO), 4.  
Contamination by a small amount of silicone grease is present. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
N
OO
(tBu)2P P(tBu)2Rh
CO
B(C6F5)3
-2-101234567891011121314
f1	(ppm)
3
6
.0
0
1.
79
0
.0
8
1.
3
0
1.
3
2
1.
3
4
5.
3
2
7.
72
 S14 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S13.  31P{1H} NMR (162 MHz, CD2Cl2) spectrum of (BCF-PyPOCOP)Rh(CO), 4. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-50-30-101030507090110130150170190210230250270290
f1	(ppm)
22
7.
8
4
22
8
.7
7
N
OO
(tBu)2P P(tBu)2Rh
CO
B(C6F5)3
 S15 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S14.  19F{1H} NMR (376 MHz, CD2Cl2) spectrum of (BCF-PyPOCOP)Rh(CO), 4. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100102030
f1	(ppm)
-1
6
4
.7
6
-1
6
4
.7
1
-1
6
4
.7
1
-1
58
.8
1
-1
58
.7
5
-1
58
.7
0
-1
3
2.
11
N
OO
(tBu)2P P(tBu)2Rh
CO
B(C6F5)3
 S16 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S15.  13C{1H} NMR (101 MHz, CD2Cl2) of (BCF-PyPOCOP)Rh(CO), 4. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-100102030405060708090100110120130140150160170180190200210
f1	(ppm)
1.
17
14
.2
3
22
.7
5
28
.2
8
28
.3
2
28
.3
5
3
4
.5
4
4
0
.5
0
4
0
.5
8
4
0
.6
7
53
.3
0
53
.5
7
53
.8
4
54
.1
1
54
.3
8
12
3
.0
0
12
5.
6
2
12
8
.5
4
12
9
.3
5
13
6
.1
6
13
8
.5
2
14
1.
4
3
14
7.
10
14
9
.5
2
16
5.
9
6
16
6
.0
4
16
6
.1
3
16
6
.2
2
16
6
.3
3
19
8
.7
9
19
9
.3
8
N
OO
(tBu)2P P(tBu)2Rh
CO
B(C6F5)3
 S17 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S16.  1H NMR (400 MHz, C6D6) spectrum of (BCF-PyPOCOP)NiBr, 5.  Contamination 
by water is present.   
  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-101234567891011121314
f1	(ppm)
3
6
.0
0
2.
0
2
0
.4
2
1.
19
1.
21
1.
23
7.
16
8
.0
8
N
O O
(tBu)2P Ni P(tBu)2
Br
B(C6F5)3
 S18 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S17.  31P{1H} NMR (162 MHz, C6D6) spectrum of (BCF-PyPOCOP)NiBr, 5. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-50-30-101030507090110130150170190210230250270290
f1	(ppm)
20
6
.3
1
N
O O
(tBu)2P Ni P(tBu)2
Br
B(C6F5)3
 S19 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S18.  1H NMR (400 MHz, CD2Cl2) spectrum of (BCF-PyPOCOP)NiBr, 5.  
Contamination by a small amount of silicone grease is present. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-2-101234567891011121314
f1	(ppm)
3
6
.0
0
2.
3
2
0
.0
9
1.
4
8
1.
50
1.
52
5.
3
2
7.
6
5
N
O O
(tBu)2P Ni P(tBu)2
Br
B(C6F5)3
 S20 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S19.  31P{1H} NMR (162 MHz, CD2Cl2) spectrum of (BCF-PyPOCOP)NiBr, 5. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-40-30-20-100102030405060708090100110120130140150160170180190200210220230240
f1	(ppm)
20
4
.9
0
N
O O
(tBu)2P Ni P(tBu)2
Br
B(C6F5)3
 S21 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S20.  19F{1H} NMR (376 MHz, CD2Cl2) spectrum of (BCF-PyPOCOP)NiBr, 5. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100102030
f1	(ppm)
-1
6
3
.1
0
-1
6
3
.0
8
-1
6
3
.0
4
-1
6
3
.0
2
-1
6
2.
9
8
-1
55
.7
9
-1
55
.7
3
-1
55
.6
8
-1
3
2.
0
6
N
O O
(tBu)2P Ni P(tBu)2
Br
B(C6F5)3
 S22 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S21.  13C{1H} NMR (101 MHz, CD2Cl2) of (BCF-PyPOCOP)NiBr, 5.  Contamination by 
a small amount of silicone grease is present.   
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-100102030405060708090100110120130140150160170180190200210
f1	(ppm)
1.
18
28
.1
4
28
.1
7
28
.2
0
4
1.
0
2
4
1.
0
9
4
1.
15
53
.3
0
53
.5
7
53
.8
4
54
.1
1
54
.3
8
12
3
.7
0
13
6
.1
2
13
6
.2
7
13
6
.4
6
13
8
.5
9
13
8
.7
7
13
8
.9
4
13
9
.1
5
14
1.
6
3
14
7.
0
6
14
9
.4
6
15
2.
11
15
2.
29
15
2.
4
8
16
6
.6
7
16
6
.7
7
16
6
.8
7
N
O O
(tBu)2P Ni P(tBu)2
Br
B(C6F5)3
 S23 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S22.  1H NMR (400 MHz, CD2Cl2) spectrum of (PyPOCOP)NiBr, 6.  Contamination by 
a small amount of silicone grease is present. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-2-101234567891011121314
f1	(ppm)
3
6
.0
0
1.
9
3
0
.0
8
1.
4
8
1.
50
1.
52
5.
3
2
7.
73
N
O O
(tBu)2P Ni P(tBu)2
Br
 S24 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S23.  31P{1H} NMR (162 MHz, CD2Cl2) spectrum of (PyPOCOP)NiBr, 6. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-50-30-101030507090110130150170190210230250270290
f1	(ppm)
19
5.
8
4
N
O O
(tBu)2P Ni P(tBu)2
Br
 S25 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S24. 13C{1H} NMR (101 MHz, CD2Cl2) of (PyPOCOP)NiBr, 6.  Contamination by a 
small amount of silicone grease is present. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
N
O O
(tBu)2P Ni P(tBu)2
Br
-100102030405060708090100110120130140150160170180190200210
f1	(ppm)
1.
17
28
.2
6
28
.2
9
28
.3
2
4
0
.2
4
4
0
.3
1
4
0
.3
8
53
.3
0
53
.5
7
53
.8
4
54
.1
1
54
.3
8
12
6
.7
6
13
8
.0
9
13
8
.2
8
13
8
.4
8
16
6
.6
3
16
6
.7
3
16
6
.8
2
 S26 
 Infrared Spectra 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S25.  IR spectrum (ATR-IR, thin film THF) of (BCF-PyPOCOP)Rh(CO), 4. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
N
OO
(tBu)2P P(tBu)2Rh
CO
B(C6F5)3
 S27 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Figure S26.  IR spectrum (ATR-IR, thin film THF) of (PyPOCOP)Rh(CO), 3. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
N
OO
(tBu)2P P(tBu)2Rh
CO
 S28 
Cyclic Voltammetry 
 
 
 
Figure S27.  Cyclic voltammogram of complex 5 in CH2Cl2 with 0.1 M (n-Bu4N)(PF6) 
electrolyte.  E1/2 = 1.68 V and Eox = 1.74 V vs. decamethylferrocene.   
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-10
-5
0
5
10
15
20
25
1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9
Cu
rr
en
t (
𝛍 A
)
Potential (V) vs. FeCp*2
N
O O
(tBu)2P Ni P(tBu)2
Br
B(C6F5)3
 S29 
 
 
Figure S28.  Cyclic voltammogram of complex 6 in CH2Cl2 with 0.1 M (n-Bu4N)(PF6) 
electrolyte. Eox = 1.749V vs. decamethylferrocene.   
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
-2
0
2
4
6
8
10
12
14
1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9
Cu
rr
en
t (
µA
)
Potential vs. FeCp*2
N
O O
(tBu)2P Ni P(tBu)2
Br
 S30 
X-Ray Structure Determination 
 
 
Compound 5 (BCF-PyPOCOP)NiBr 
 
Low-temperature diffraction data (f-and w-scans) were collected on a Bruker AXS D8 
VENTURE KAPPA diffractometer coupled to a PHOTON 100 CMOS detector with Mo Ka 
radiation (l = 0.71073 Å) from an IμS micro-source for the structure of compound 5. The structure 
was solved by direct methods using SHELXS and refined against F2 on all data by full-matrix least 
squares with SHELXL-2016 using established refinement techniques.1-3All non-hydrogen atoms 
were refined anisotropically. All hydrogen atoms were included into the model at geometrically 
calculated positions and refined using a riding model. The isotropic displacement parameters of 
all hydrogen atoms were fixed to 1.2 times the U value of the atoms they are linked to (1.5 times 
for methyl groups).  
Compound 5 crystallizes in the monoclinic space group P21/n with one molecule in the 
asymmetric unit.  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 S31 
Empirical formula  C39 H38 B Br F15 N Ni O2 P2 
Formula weight  1049.07 
Temperature  100(2) K 
Wavelength  0.71073 Å 
Crystal system  Monoclinic 
Space group  P21/n 
Unit cell dimensions        a=18.331(2) Å
 a= 90°. 
 b = 12.0823(15) Å b= 99.077(5)°. 
 c = 19.875(3) Å g = 90°. 
Volume 4346.9(9) Å3 
Z  4 
Density (calculated) 1.603 Mg/m3 
Absorption coefficient 1.539 mm-1 
F(000) 2112 
Crystal size 0.450 x 0.450 x 0.400 mm3 
Theta range for data collection 2.250 to 36.417°. 
Index ranges -28<=h<=30, -20<=k<=20, -33<=l<=33 
Reflections collected 151341 
Independent reflections 21162 [R(int) = 0.0554] 
Completeness to theta = 25.242° 99.9 %  
Absorption correction Semi-empirical from equivalents 
Max. and min. transmission 0.7471 and 0.6178 
Refinement method Full-matrix least-squares on F2 
Data / restraints / parameters 21162 / 0 / 571 
Goodness-of-fit on F2 1.025 
Final R indices [I>2sigma(I)] R1 = 0.0357, wR2 = 0.0693 
R indices (all data) R1 = 0.0611, wR2 = 0.0765 
Extinction coefficient n/a 
Largest diff. peak and hole 0.918 and -0.964 e.Å-3 
 
 
Table S1.  Crystal data and structure refinement for complex 5. 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 S32 
References 
 
1. Sheldrick, G.M. Phase Annealing in SHELX-90: Direct Methods for Larger Structures. 
Acta. Cryst. 1990, A46, 467-473. 
 
2. Sheldrick, G.M. A Short History of SHELX. Acta. Cryst. 2008, A64, 112-122. 
 
3.         Müller, P. Practical Suggestions for Better Crystal Structures. Crystallography Reviews     
2009, 15, 57-83. 
 
 
 
 


Synthesis and Characterization of 3,5-Bis(di-tert-butylphosphinito)pyridine Pincer Complexes

https://authors.library.caltech.edu/104184/2/om0c00270_si_001.pdf

Synthesis and Characterization of 3,5-Bis(di-tert-butylphosphinito)pyridine Pincer Complexes

Abstract

Similar works

Full text

Available Versions

Caltech Authors - Main

Caltech Authors - Main