Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

Chapitre V
Synthesis of [Co{bis(1-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)-1-
ethylethyl)phenylphosphonite}Cl2] 16
Anhydrous CoCl2 (0.14 g, 1.1 mmol) was added to a solution of NOPON Me2 (0.46 g, 1.1
mmol) in 30 mL of THF. The blue solution was for stirred 3 h at room temperature. After
elimination of THF under reduced pressure, the blue powder was dried overnight under
vacuum. Complex 16 was obtained as a blue powder without further purification (yield: 0.58
g, 1.05 mmol, 97%). The structure of 16 has been determined by X-ray diffraction on single
crystals obtained by low diffusion of toluene into a CH2Cl2 solution. IR (KBr): 1682 (s), 1627
(vs), 1465 (m), 1437 (m), 1366 (m), 1313 (m), 1258 (w), 1144 (s), 1177 (w), 1142 (m), 1119
(vs), 1021 (s), 979 (vs), 913 (m), 865 (w), 741 (s), 714 (w), 698 (w), 576 (w), 562 (w) cm -1 .
Anal. Calc. for C22H33Cl2CoN2O4P: C, 48.01; H, 6.04; N, 5.09. Found: C, 48.06; H, 5.92; N,
4.84.
Synthesis of [Co{phenyl-bis(2-picolyl)phosphine}Cl2] 17.
Anhydrous CoCl2 (0.12 g, 0.9 mmol) was added to a solution of phenyl-bis(2-
picolyl)phosphine 1 (0.27 g, 0.9 mmol) in 20 mL of MeOH. The green solution was stirred
overnight at room temperature. After elimination of MeOH under reduced pressure, the
residue was dissolved in 5 mL of CH2Cl2 and the solution was filtered. After elimination of
the solvent under reduced pressure, the green complex 17 was washed with 20 mL of
diethylether and dried overnight under vacuum (yield: 0.34 g, 0.8 mmol, 87%).
IR (KBr): 1603 (s), 1478 (s), 1437 (s), 1315 (s), 1164 (m), 1107 (m), 749 (s), 694 (m) cm -1 .
Anal. Calcd.: for C18H17Cl2CoN2P: C, 51.21; H, 4.06; N, 6.64. Found: C, 50.45; H, 4.29; N,
5.92.
Synthesis of [Co{bis(2-oxazoline-2-ylmethyl)phenylphosphine}Cl2] 18
Anhydrous CoCl2 (0.14 g, 1.1 mmol) was added to a solution of (2-oxazoline-2-
ylmethyl)phenylphosphine 2 (0.305 g, 1.1 mmol) in 30 mL of THF. Complex 18 precipitated
as a blue powder and the solution was stirred overnight at room temperature. After
elimination of THF under reduced pressure, the blue powder was dried overnight under
vacuum. Complex 18 was obtained as a blue powder without further purification (yield: 0.43
g, 1.05 mmol, 96%). IR (KBr): 1644 (vs), 1620 (vs sh), 1478 (m), 1435 (s), 1420 (s), 1384 (s),
1330 (m), 1264 (s), 1200 (m), 1190 (m sh), 1143 (m), 1130 (m sh), 1020 (w sh), 1002 (s), 933
(s), 855 (w), 795 (w), 749 (m), 697 (w) cm -1 .
31