Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

Chapitre II
7.22. Found: C, 36.97; H, 6.13; N, 6.68. IR (KBr): 1674 (s), 1637(vs), 1508 (w), 1467 (m),
1450 (m sh), 1406(m), 1371 (m), 1281 (s), 1209 (m), 1185 (w sh), 1063 (vs), 952 (s), 843 (w)
cm -1 .
Synthesis of [Ni(µ-Cl)2{(pyridin-2-yl) methanol}2]2Cl2 (15)
Complex 15 was prepared by reaction of NiCl2 (0.86 g, 6.6 mmol) and (4,5-dihydro-
4,4-dimethyloxazol-2-yl)methanol (1.44 g, 13.2 mmol) by following the same procedure
described for 14 and it was isolated as a green powder. Yield: 2.18 g (95%). Single crystals
suitable for X-ray diffraction were obtained by slow diffusion of petroleum ether into a
CH2Cl2 solution of 15. Anal. Calcd. for C24H28Cl4N4Ni2O4: C, 41.43; H, 4.06; N, 8.05.
Found: C, 41.25; H, 4.48; N, 7.61. HRMS: Mass Calcd for C12H14ClN2NiO2: 311.0092.
Found: 311.0099 (Ni(N,O)2Cl) + . IR (KBr): 1608 (vs), 1571 (s), 1483 (s), 1444 (s), 1440 (s
sh), 1349 (w), 1286 (s), 1237 (m), 1156 (s), 1065 (s sh), 1050 (s sh), 1033 (vs), 778 (s sh),
765 (s), 727 (m), 648 (m), 626 (w) cm -1 .
Synthesis of [Ni{(pyridin-2-yl)methanol}3Cl2] (17)
To a solution of NiCl2 (0.70 g, 5.4 mmol) in 30 mL of methanol was added a solution
of 4 equiv. of (pyridin-2-yl)methanol (2.00 g, 21.6 mmol) in 5 mL of methanol and the
reaction mixture was stirred overnight at room temperature. At the end of the reaction, the
methanol was removed under reduced pressure and the residue was washed with diethylether
(3x20 mL) to eliminate unreacted (pyridin-2-yl)methanol and dried under reduced pressure.
The product was isolated as a blue powder. Yield: 2.05 g (93%). Single crystals of 17·CH2Cl2
suitable for X-ray diffraction were obtained by slow diffusion of pentane into a CH2Cl2
solution. Anal. Calcd. for C18H21Cl2N3NiO3: C, 47.31; H, 4.63; N, 9.20. Found: C, 47.10; H,
4.96; N, 8.51. IR (KBr): 1608 (vs), 1571 (s), 1483 (s), 1444 (s), 1440 (s sh), 1349 (w), 1286
(s), 1237 (m), 1156 (s), 1065 (s sh), 1050 (s sh), 1033 (vs), 778 (s sh), 765 (s), 727 (m), 648
(m), 626 (w) cm -1 .
Synthesis of [Ni{(pyridin-2-yl) methanol}{(pyridin-2-yl) methanolate}Cl] (20)
To a suspension of 15 (1.50 g, 4.3 mmol) in THF was added excess NaH (1.00 g, 41.7
mmol) and the mixture was stirred for 24 h at room temperature. At the end of the reaction,
the solvent was removed under reduced pressure and 20 mL of CH2Cl2 was added. The green
solution obtained was filtered to eliminate unreacted NaH and 15. After removing the solvent
under reduced pressure, 20 was washed with diethylether, dried under vacuum and isolated as
21