Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

Chapitre VI
the mixture was stirred overnight at room temperature. After reaction, the red solution was
evaporated under reduced pressure to afford the pale yellow complex 15. The 1 H NMR
spectrum indicated a yield of 83% based on [Ni(COD)2]. 1 H NMR (300 MHz, C6D6): δ 1.22
(9H, br d, 3 JPC = 13.5 Hz, CH3), 5.11 (1H, br s, P-CH), 6.7-7.8 (30H, br m, aromatic H);
31 P{ 1 H} NMR (C6D6, 121.5 MHz): AB spin system δA 31.4 (d, PPh(t-Bu), 2 JAB = 278 Hz), δB
22.4 (d, PPh3, 2 JAB = 278 Hz).
[NiPh{(n-Bu) 2PCH⋅⋅⋅C(⋅⋅⋅O)Ph}(PPh 3)] 16
A solution of 0.890 g (3.24 mmol) of [Ni(COD)2] in 50 mL of toluene was added to a
solution of 0.850 g (3.24 mmol) of PPh3 and 1.102 g (3.24 mmol) of 9 in 50 mL of toluene at
0 °C and the mixture was stirred for 3 days at room temperature. After reaction, the brown
solution was evaporated under reduced pressure to afford complex 16 as a brown oil. The 1 H
NMR spectrum indicated a yield of 84% based on [Ni(COD)2]. 1 H NMR (300 MHz, C6D6): δ
0.86 (6H, t, 3 JHH = 7.2 Hz, CH3), 1.67 (12H, br m, CH2), 4.60 (1H, s, PCH), 6.78-7.83 (25H,
br m, aromatic H); 31 P{ 1 H} NMR (C6D6, 121.5 MHz): AB spin system δA 22.6 (d, PPh(t-Bu),
2 JAB = 280 Hz), δB 21.4 (d, PPh3, 2 JAB = 280 Hz).
[NiPh{Ph(n-Bu)PCH⋅⋅⋅C(⋅⋅⋅O)Ph}(PPh 3)] 17
A solution of 0.078 g (0.28 mmol) of [Ni(COD)2] in 5 mL of toluene was added to a
solution of 0.073 g (0.28 mmol) of PPh3 and 0.104 g (0.28 mmol) of 10 in 5 mL of toluene at
0 °C and the mixture was stirred overnight at room temperature. After reaction, the yellow
solution was evaporated under reduced pressure to afford complex 17 as a pale yellow
powder. The 1 H NMR spectrum indicated a yield of 43% based on 10. 1 H NMR (300 MHz,
C6D6): δ 0.70-1.75 (9H, broad signals corresponding of the n-butyl substituents), 4.90 (1H, s,
PCH), 6.78-7.99 (25H, br m, aromatic H), 8.39 (5H, br s, aromatic H); 31 P{ 1 H} NMR (C6D6,
121.5 MHz): AB spin system δA 22.3 (d, PPh(t-Bu), 2 JAB = 282 Hz), δB 20.4 (d, PPh3, 2 JAB =
282 Hz).
[NiPh{Ph 2PCH⋅⋅⋅C(⋅⋅⋅O)Ph}(Py)] 18 36
A solution of 0.092 g (0.33 mmol) of [Ni(COD)2] in 5 mL of toluene was added to a
solution of 0.127 g (0.33 mmol) of 3 and 1 mL of pyridine (12.66 mmol) in 5 mL of toluene
and the mixture was stirred overnight at room temperature. After reaction, the complex 18
was isolated as a pale yellow powder after filtration of the dark suspension and elimination of
19