Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

Chapitre V
IR (KBr): 1658 (vs), 1478 (w), 1437 (m), 1402 (s), 1374 (m), 1339 (w), 1270 (s), 1168 (s),
1108 (w), 1034 (s), 999 (w), 972 (w), 932 (m), 868 (w), 749 (m), 694 (m) cm -1 .
Anal. Calc. for C14H17Cl2N2NiO2P: C, 41.43; H, 4.22; N, 6.90. Found: C, 40.43; H, 4.42; N,
6.52.
Synthesis of [Ni{bis(2-oxazolin-2,5,5-trimethyl)phenylphosphine}Cl2] 8
A solution of 2.42 g (7.3 mmol) bis(2-oxazolin-2,5,5-trimethyl)phenylphosphine 3 in 50 mL
of Methanol was stirred while 0.94 g (7.3 mmol) NiCl2 in 50 mL of methanol was added drop
wise to the solution. After several hours the solvent was evaporated and 10 mL of dried and
degassed CH2Cl2 was added to the red oil. Petroleum ether was added to the solution to
precipitate the green complex. After treating the suspension with ultrasound for 30 minutes
the complex was filtered and washed several times with diethylether. Green complex 8 was
dried several hours in vacuum (yield: 2.60 g, 5.6 mmol, 77 %).
IR (KBr): 1636 (vs), 1464 (m), 1437 (m), 1403 (m), 1369 (s), 1320 (vs), 1162 (s), 1107 (m),
1028 (w), 999 (s), 955 (s), 863 (w), 840 (w), 747 (s), 695 (s) cm -1 .
Anal. Calc. for C18H25Cl2N2NiO2P: C, 46.80; H, 5,45; N, 6.06. Found: C, 46.51; H, 5.58; N:
5.77. Mass Calcd for C18H25ClN2NiO2P : 425.0696. Found. 425.0641 [Ni(N,P,N)Cl] + .
Synthesis of [Ni{bis((pyridin-2-yl)methyl)phenylphosphonite}Cl2] 9
To a solution of ligand bis((pyridin-2-yl)methyl)phenylphosphonite 4 in 30 mL of CH2Cl2
(0.42 g, 1.3 mmol) was added 0.30 g (1.3 mmol) of [NiCl2(DME)]. The dark green solution
was stirred overnight at room temperature. After complexation, the solution was concentrated
to 5 ml and filtered. 50 mL of petroleum ether was added to the solution to precipitate the
complex. After filtration by canula, the green complex was washed with 20 ml of diethylether
and dried under vacuum overnight (yield: 0.51 g, 1.2 mmol, 87 %).
IR (KBr) : 1603 (vs), 1571 (m), 1483 (s), 1463 (s), 1445 (vs), 1385 (w), 1315 (s), 1231 (m),
1164 (m), 1115 (m), 1026 (vs), 995 (vs sh), 836 (s), 800 (s), 770 (s), 734 (s), 713 (m), 691
(m), 626 (s),548 (s), 485 (m), 431 (m) cm -1 . Anal. Calcd.: for C18H17Cl2N2NiO2P: C, 47.63;
H, 3.77; N, 6.17. Found: C, 47.98; H, 4.21; N, 5.85. HRMS : Mass Calcd for
C18H17ClN2NiO2P : 417.0064. Found. 417.0070 [Ni(N,P,N)Cl] + .
Synthesis of [Fe{phenyl-bis(2-picolyl)phosphine}2{FeCl3OFeCl3}] 10
To a solution of phenyl-bis(2-picolyl)phosphine 1 (2.40 g, 8.2 mmol) in 50 mL of CH2Cl2
was added a CH2Cl2 solution of FeCl2·4H2O (1.63 g, 8.2 mmol) and the mixture was stirred at
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