Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

Chapitre V
To a solution of (2-oxazolin-2,5,5-trimethyl)phenylphosphine 3 (1.05 g, 3.15 mmol) in
CH2Cl2 was added [Pd(Me)Cl(COD)] (0.84 g, 3.15 mmol) at room temperature and the pale
yellow solution was stirred overnight. After elimination of the solvent under reduced pressure,
a pale yellow powder was obtained. Complex 13 was washed with diethylether and dried
under vacuum (yield: 1.34 g, 2.7 mmol, 87%).
IR (KBr): 1659 (s), 1630 (s), 1463 (m), 1435 (m), 1366 (s), 1320 (s), 1261 (s), 1159 (s), 1103
(s), 951 (m), 801 (s), 747 (m), 692 (m) cm -1 .
1 H NMR (300 MHz, CDCl3): δ 0.74 (3H, s, Pd-CH3) 1.27 (3H, s, CCH3) 1.30 (3H, s, CCH3)
1.56 (3H, s, CCH3) 1.58 (3H, s, CCH3), ABX spin system 1 (A = B = H, X = P) 2.98 (1H, 2 jAB
= 18.0 Hz, 2 JPA = 11.1 Hz, PCHAHB), ABX spin system 2 (A = B = H, X = P) 3.06 (1H, 2 JAB
= 14.4 Hz, 2 jPA = 7.5 Hz, PCHAHB), ABX spin system 2 (A = B = H, X = P) 3.23 (1H, 2 JAB =
14.4 Hz, 2 JPB = 12.9 Hz, PCHAHB), ABX spin system 1 (A = B = H, X = P) 3.78 (1H, 2 JAB =
18.0 Hz, 2 jPB = 11.1 Hz, PCHAHB), AB spin system 3.97 and 4.01 (2H, 2 JAB = 8.1 Hz,
overlapping signal of OCHAHB), AB spin system 4.13 and 4.16 (2H, 2 JAB = 8.1 Hz,
overlapping signal of OCHAHB), 7.67 – 7.84 (5H, m, aromatic H); 13 C{ 1 H} NMR (75.5 MHz,
CDCl3): δ -4.3 (s, Pd-CH3), 26.1 (d, 1 JPC = 25.1 Hz, PCH2), 27.6 (s, C-CH3), 27.9 (s, C-CH3),
28.2 (s, C-CH3), 28.6 (s, C-CH3), 30.0 (d, 1 JPC = 30.0 Hz, PCH2), 67.9 (s, NCCH3), 68.4 (s,
NCCH3), 79.6 (s, OCH2), 83.5 (s, OCH2), 129.2 (d, 2 JPC = 11.3 Hz, m-CH of aryl), 129.3 (d,
1 JPC = 48.6 Hz, C-P of aryl), 132.1 (s, p-CH of aryl), 132.7 (d, 3 JPC = 13.5 Hz, o-CH of aryl),
159.4 (s, C=N from uncoordinated oxazoline), 169.5 (d, 2 JPC = 18.5 Hz, C=N from
coordinated oxazoline); 31 P{ 1 H} NMR (121.5 MHz , CDCl3): δ 26.56.
Synthesis of [Pd{bis(2-oxazolin-2,5,5-trimethyl)phenylphosphine}Cl2] 14
To a solution of (2-oxazolin-2,5,5-trimethyl)phenylphosphine 3 (0.80 g, 2.4 mmol) in CH2Cl2
was added 0.92 g (2.4 mmol) of [PdCl2(NCPh)2] at room temperature and the red solution was
stirred overnight. After elimination of the solvent under reduced pressure, a yellow powder
was obtained. After washing with 20 mL of THF, the pale yellow powder was dried overnight
under vacuum (yield: 1.01 g, 2.0 mmol, 83%).
IR (KBr): 1659 (s), 1630 (s), 1463 (m), 1435 (m), 1419 (w), 1366 (s), 1320 (s), 1261 (s),
1159 (s), 1103 (s), 951 (m), 801 (s), 747 (m), 692 (m) cm -1 .
1 H NMR (300 MHz, CDCl3): δ 1.22 (3H, s, CCH3) 1.28 (3H, s, CCH3) 1.67 (3H, s, CCH3)
1.71 (3H, s, CCH3) ABX spin system 1 (A = B = H, X = P) 3.23 (1H, 2 JAB = 18.7 Hz, 2 JPA =
12.7 Hz, PCHAHB of coordinated oxazoline), ABX spin system 2 (A = B = H, X = P) 3.49
(1H, JAB = 16.4 Hz, 2 JPA = 12.4 Hz, PCHAHB of uncoordinated oxazoline), ABX spin system 2
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