J. Guenther, et al.
Molecular Catalysis 479 (2019) 110629
Tris(7-diphenylphosphinoheptyl)ethoxysilane 5
2.01–2.06 (m, 6H, H11), 1.37–1.48 (m, 12H, overlapping H2, H10),
3
1
1
1
.20–1.35 (m, 42H, overlapping H3-H9), 1.17 (t, J( H- H) =6.9 Hz,
13 1
3
H, H13), 0.55-0.61 (m, 6H, H1); C{ H} NMR (CDCl , 125.7 MHz): δ
2 31 13
3
1
31 13
(
ppm) = 139.05 (d, J( P- C) =13.0 Hz, C
i
), 132.67 (d, J( P- C)
3
31 13
=
18.3 Hz, C
o
), 128.38 (C
p
), 128.32 (d, J( P- C) =6.5 Hz, C ), 58.35
m
1
31 13
(
C12), 33.70 (C3), 31.23 (d, J( P- C) =12.9 Hz, C11), 29.66 (C4*),
The ethoxysilane
.572 mmol) and Ph
2
(480 mg, 1.316 mmol), AIBN (94 mg,
3
2
9.59 (C5*), 29.52 (C6*), 29.31 (C7*), 29.28 (C8*), 28.04 (d,
J
0
2
PH (942 mg, 5.060 mmol) are combined in a
31 13
2
31 13
(
P- C) =11.0 Hz, C9), 25.96 (d, J( P- C) =15.9 Hz, C10), 23.19
31 1
Schlenk flask, heated to 70 °C and stirred for 5 d. The conversion is
(
C2), 18.67 (C13), 13.66 (C1), *assignments interchangeable; P{ H}
29 1
3
1
monitored by P NMR of the reaction mixture. After completion of the
reaction the crude product is purified by column chromatography
NMR (CDCl
3
, 202.3 MHz): δ (ppm) = −16.33 (s); Si{ H} NMR
(
CDCl , 79.4 MHz): δ (ppm) = 15.53 (s).
3
(
SiO , toluene) and 5 (538 mg, 0.582 mmol) is obtained as a colorless
2
viscous oil in 44% yield.
1
3
31
1
H NMR (C D
6
6
, 499.7 MHz): δ (ppm) = 7.45 (dd, J( P- H)
), 7.03–7.12 (m, 18H, H , H ),
.64 (q, J( H- H) =6.9 Hz, 2H, H8), 1.95–2.00 (m, 6H, H7), 1.42–1.51
m, 12H, H6*, H5*), 1.31–1.39 (m, 12H, H4*, H3*), 1.24–1.31 (m, 6H,
H2), 1.18 (t, J( H- H) =6.9 Hz, 3H, H9), 0.66-0.71 (m, 6H, H1),
Hexakis(11-diphenylphosphinoundecyl)disiloxane 6d
3
1
1
=
6.9 Hz, J( H- H) =6.9 Hz, 12H, H
o
m
p
3
1
1
3
(
3
1
1
1
3
1
*
assignments interchangeable; C{ H} NMR (C
6
D , 125.7 MHz): δ
6
1
31 13
2 31 13
(
ppm) = 140.02 (d, J( P- C) =14.7 Hz, C
i
), 133.14 (d, J( P- C)
The disiloxane 3b (628 mg, 0.633 mmol), AIBN (140 mg,
3
31 13
31 13
=
18.5 Hz, C
o
), 128.67 (d, J( P- C) =6.4 Hz, C ), 128.59 (C ), 58.52
m
p
0.853 mmol) and Ph PH (1.151 g, 6.086 mmol) are combined in a
2
3
(
C8), 34.06 (C3), 31.59 (d, J( P- C) =12.6 Hz, C5), 29.42 (C4),
Schlenk flask, heated to 70 °C and stirred for 4 d. When complete
1
31 13
2
1
31 13
31
2
8.63 (d, J( P- C) =12.4 Hz, C7), 25.51 (d, J( P- C) =16.3 Hz,
conversion is reached, as monitored by P NMR of the reaction mix-
3
1
C6), 23.76 (C2), 18.67 (C9), 14.26 (C1);
P{ H} NMR (C
6
D
6
,
ture, the crude product is purified by column chromatography (SiO ,
2
2
9
1
2
02.3 MHz): δ (ppm) = -16.38 (s); Si{ H} NMR (C
6
D
6
, 79.4 MHz): δ
toluene) to give 6 (950 mg, 0.450 mmol) as a colorless viscous oil in
(
ppm) = 13.93 (s).
71% yield.
1
H NMR (CDCl
3
, 499.7 MHz): δ (ppm) = 7.44–7.52 (m, 24H, H
, H ), 2.06–2.14 (m, 12H, H11), 1.26–1.58 (m,
08H, overlapping H2-H10), 0.61-0.69 (m, 12H, H1); C{ H} NMR
o
),
7
1
.28–7.41 (m, 36H, H
m
p
Hexakis(7-diphenylphosphinoheptyl)disiloxane 5d
1
3
1
1
31 13
31 13
(
CDCl
3
, 125.7 MHz): δ (ppm) = 139.03 (d, J( P- C) =13.3 Hz, C
i
),
2
31 13
3
1
32.65 (d, J( P- C) =17.9 Hz, C
), 128.17 (C ), 33.59 (C3), 31.19 (d, J( P- C) =12.2 Hz, C11),
9.61 (C4*), 29.53 (C5*), 29.48 (C6*), 29.31 (C7*), 29.25 (C8*), 28.02
o
), 128.29 (d, J( P- C) =7.9 Hz,
1
31 13
C
m
p
2
3
31 13
2
31 13
(
d, J( P- C) =11.6 Hz, C9), 25.94 (d, J( P- C) =14.8 Hz, C10),
The disiloxane 2b (465 mg, 0.709 mmol), AIBN (88 mg,
.535 mmol) and Ph PH (1.187 g, 6.376 mmol) are combined in a
31
1
2
3.07 (C2), 15.06 (C1), *assignments interchangeable; P{ H} NMR
, 202.3 MHz): δ (ppm) = −16.34 (s).
0
2
(
CDCl
3
Schlenk flask, heated to 70 °C and stirred for 5 d. The conversion is
3
1
monitored by P NMR of the reaction mixture. Upon completion of the
reaction the crude product is purified by column chromatography
Rhodium complex 15
(
SiO , toluene : ethylacetate = 9 : 1) to give 5d (855 mg, 0.502 mmol)
2
as a colorless viscous oil in 70% yield.
1
H NMR (C
6
D
6
, 499.7 MHz): δ (ppm) = 7.44–7.49 (m, 24H, H ),
o
7
1
1
.03–7.14 (m, 36H, H
m
, H ), 1.96–2.01 (m, 12H, H7), 1.43–1.53 (m,
p
2H, H6*), 1.34–1.42 (m, 24H, H5*, H4*), 1.27–1.34 (m, 12H, H3*),
RhClpyCOD (35 mg, 0.107 mmol) is dissolved in 10 ml of CH
2
Cl .
2
.20–1.27 (m, 12H, H2), 0.56-0.61 (m, 12H, H1), *assignments inter-
1
3
1
1
Ligand 6 (39 mg, 0.036 mmol), dissolved in CH Cl (15 ml), is added
2
2
changeable; C{ H} NMR (C
6
D
6
, 125.7 MHz): δ (ppm) = 140.01 (d, J
3
1
13
2
31 13
dropwise and the reaction mixture is stirred at RT for 4 h. Then the
solvent is removed in vacuo and the residue washed with copious
amounts of pentane. After drying the residue in vacuo 11 (50 mg,
0.021 mmol) is obtained as an orange powder in 60% yield.
(
(
(
P- C) =14.6 Hz, C
i
), 133.14 (d, J( P- C) =18.5 Hz, C ), 128.68
o
3
31 13
3
d, J( P- C) =6.4 Hz, C
m
), 128.60 (C ), 33.95 (C3), 31.55 (d, J
p
3
1
13
1 31 13
P- C) =12.5 Hz, C5), 29.42 (C4), 28.63 (d, J( P- C) =12.3 Hz,
2
31 13
31
C7), 25.51 (d, J( P- C) =16.2 Hz, C6), 23.58 (C2), 15.62 (C1);
P
1
1
H NMR (CDCl , 499.7 MHz): δ (ppm) = 7.59–7.65 (m, 12H, H ),
3
o
{
H} NMR (C
6
D , 202.3 MHz): δ (ppm) = −16.38 (s).
6
3
7
(
.34–7.41 (m, 18H, H
m
, H ), 5.46 (s, 6H, COD-HOlefin), 3.65 (q, J
p
1
1
H- H) =6.9 Hz, 2H, CH O), 2.99 (s, 6H, COD-HOlefin), 2.43–2.50 (m,
2
Tris(11-diphenylphosphinoundecyl)ethoxysilane 6
6
H, H11), 2.23–2.41 (m, 12H, COD-Halkyl), 1.96–2.05 (m, 6H, H11),
1
.76–1.89 (m, 12H, COD-Halkyl), 1.37–1.45 (m, 6H, H10), 1.19–1.33
3
1
1
(
m, 48H, H2-H9), 1.15 (t, J( H- H) =6.9 Hz, 3H, CH
3
), 0.52-0.59 (m,
1
3
1
2
6
H, H1); C{ H} NMR (CDCl
3
, 125.7 MHz): δ (ppm) = 133.51 (d,
J
3
1
13
1
31 13
(
P- C) =12.2 Hz, C
o
), 132.35 (d, J( P- C) =39.5 Hz, C
i
), 129.88
4
31 13
3
31 13
(
d, J( P- C) =2.1 Hz, C
p
), 128.08 (d, J( P- C) =9.4 Hz, C ),
m
The ethoxysilane
.634 mmol) and Ph
3
(375 mg, 0.703 mmol), AIBN (104 mg,
1
103
13
2
31 13
1
7
04.35 (dd, J( Rh- C) =12.6 Hz, J( P- C) =6.4 Hz, COD-Colefin),
0
2
PH (575 mg, 3.040 mmol) are combined in a
1
103
13
31 13
0.10 (d, J( Rh- C) =6.8 Hz, COD-Colefin), 58.29 (CH
2
O), 33.68
Schlenk flask, heated to 70 °C and stirred for 4 d. The conversion is
3
2
31 13
3
1
(
C3), 32.91 (d, J( P- C) =2.3 Hz, C9), 31.44 (d, J( P- C)
monitored by P NMR of the reaction mixture. After the reaction is
complete, the crude product is purified by column chromatography
1
=
13.5 Hz, C10), 29.58 (C4*, overlapping with COD-Calkyl), 29.56 (d, J
3
1
13
(
P- C) =8.0 Hz, C11), 29.29 (C5*), 29.14 (C6*), 28.68 (COD-Calkyl),
(
SiO , toluene) to give 6 (350 mg, 0.320 mmol) as a colorless viscous oil
2
2
7.96 (C7*), 25.98 (C8*), 23.16 (C2), 18.63 (CH ), 13.63 (C1), *in-
3
in 45% yield.
3
31
1
1
1
terchangeable assignments;
P{ H} NMR (CDCl , 202.3 MHz): δ
3
H NMR (CDCl
3
, 499.7 MHz): δ (ppm) = 7.39–7.44 (m, 12H, H ),
o
), 3.65 (q, 3J( H- H) =6.9 Hz, 2H, H12),
1
(
ppm) = 26.14 (d, 1J( Rh- P) =147.9 Hz).
103
1
7
.30–7.35 (m, 18H, H
m
, H
p
12