Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

Chapitre IV
122.3 (s, Py), 122.5 (d, 2 JPC = 6.2 Hz, PCCC), 123.4 (s, Ph), 123.5 (s, Ph), 124.9 (s, Ph),
127.7 (d, 3 JPC = 13.4 Hz, PCCHCH), 129.6 (s, Ph), 131.5 (d, 2 JPC = 48.2 Hz, PCCH), 131.7
(s, Ph), 131.9 (s, Ph), 132.2 (d, 3 JPC = 2.8 Hz, POCC), 136.5 (s, Py), 141.9 (s, Py), 149.7 (d,
2 JPC = 9.3 Hz, POC Ph), 158.1 (d, 2 JPC = 4.7 Hz, NCCH2); 31 P{ 1 H} NMR (CDCl3): δ 130.5
(s).
Chloro-di-tert-buytlphosphine. 77
It was synthesized according to the literature 77 by dropwise addition of a solution of
n-BuLi (60.0 mL, 102.0 mmol, 1.7 M in hexane) to a solution of PCl3 (7.00 g, 51.0 mmol) in
100 mL of pentane at -78 °C. The mixture was stirred overnight from -78 °C to room
temperature. LiCl was removed by filtration and pentane was slowly removed under reduced
pressure. The residue was distilled under reduced pressure (70 °C, 10 mbar) and chloro-di-
tert-butylphosphine was isolated as a colorless liquid. Yield: 2.90 g, 32%. 1 H NMR (CDCl3):
δ 1.24 (d, 18H, 3 JPH =12.1 Hz, CH3); 31 P{ 1 H} NMR (CDCl3): δ 148.0 (s).
2-methyl-oxy-(di-tert-butylphosphino)pyridine 16.
A solution of n-BuLi (4.00 mL, 6.7 mmol, 1.7 M in hexane) was added to a solution
of (pyridin-2-yl)methanol (0.725 g, 6.7 mmol) in 30 mL of THF at -78 °C. The solution
became red and was stirred for 30 min. Di-tert-butylchlorophosphine (1.20 g, 6.7 mmol) in
20 mL of THF was added to the mixture to afford a pale yellow solution which was stirred
overnight from -78 °C to room temperature. THF was removed under reduced pressure and
diethylether was added to precipitate LiCl. After filtration and removal of the solvents under
reduced pressure, 16 was isolated as a pale yellow oil. Yield: 1.52 g, 89%. 1 H NMR (CDCl3):
δ 1.13 (d, 18H, 3 JPH = 11.7 Hz, CH3), 4.93 (d, 2H, 3 JPH = 5.7 Hz, CH2), 7.18 (m, 1H, Py),
7.55 (d, 1H, 3 JHH = 7.8 Hz, Py), 7.70 (dt, 1H, 3 JHH = 7.5 Hz 4 JHH = 1.8 Hz, Py), 8.53 (d, 1H,
3 JHH = 4.8 Hz, Py); 13 C{ 1 H} NMR (CDCl3): δ 27.4 (d, 2 JPC = 15.1 Hz, CH3), 35.4 (d, 2 JPC =
24.3 Hz, PC), 76.1 (d, 2 JPC = 21.7 Hz, OCH2), 120.9 (s, Py), 122.1 (s, Py), 136.6 (s, Py),
149.0 (s, Py), 159.5 (d, 3 JPC = 10.6 Hz, NCCH); 31 P{ 1 H} NMR (CDCl3): δ 166.3 (s).
[NiCl2(DME)]. 78
NiCl2 (100 g, 771.6 mmol) was dissolved in a mixture of 300 mL of methanol and 50
mL of trimethylorthoformate and stirred at reflux overnight. After reaction, unreacted NiCl2
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