Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

Chapitre V
(A = B = H, X = P), 3.57 (1H, 2 JAB = 16.4 Hz, 2 JPB = 11.0 Hz, PCHAHB of uncoordinated
oxazoline), AB spin system 3.89 and 3.98 (1H, JAB = 8.1 Hz, overlapping signal of OCHAHB),
ABX spin system 1 (A = B = H, X = P) 4.04 (1H, 2 JAB = 18.7 Hz, 2 JPB = 11.7 Hz, PCHAHB of
coordinated oxazoline), AB spin system 4.25 and 4.34 (1H, 2 JAB = 8.4 Hz, overlapping signal
of OCHAHB), 7.67 – 7.84 (5H, m, aromatic H); 13 C{ 1 H} NMR (75.5 MHz , CDCl3): δ 26.0 (d,
1 JPC = 35.9 Hz, PCH2), 27.4 (s, C-CH3), 27.8 (s, C-CH3), 28.2 (s, C-CH3), 28.5 (s, C-CH3),
29.1 (d, 1 JPC = 33.3 Hz, PCH2), 68.0 (s, NCCH3), 69.9 (s, NCCH3), 79.5 (s, OCH2), 84.2 (s,
OCH2), 125.8 (d, 1 JPC = 56.7 Hz, C-P of aryl), 129.3 (d, 2 JPC = 12.0 Hz, o-CH of aryl), 132.5
(s, p-CH of aryl), 132.7 (d, 3 JPC = 8.1 Hz, m-CH of Aryl), 158.2 (d, 2 JPC = 7.6 Hz, C=N from
uncoordinated oxazoline), 173.9 (d, 2 JPC = 51.6 Hz, C=N from coordinated oxazoline);
31 P{ 1 H} NMR (121.5 MHz, CDCl3): δ 19.40.
Anal. Calc. for C18H25Cl2N2O2PPd: C, 42.42; H, 4.94; N, 5.50. Found: C, 41.84; H, 4.59; N,
5.45.
Synthesis of [Pd(NCCH3){bis(2-oxazolin-2,5,5-trimethyl)phenylphosphine}(BF4)2] 15
To a solution of (2-oxazolin-2,5,5-trimethyl)phenylphosphine 3 (0.45 g, 1.4 mmol) in CH2Cl2
was added 0.61 g (1.4 mmol) of [Pd2(MeCN)4(BF4)] at room temperature and the red solution
was stirred overnight. After elimination of the solvent under reduced pressure, an orange
powder was obtained which was washed with 20 mL of diethylether and dried overnight
under vacuum (yield: 0.82 g, 1.25 mmol, 90%).
IR (KBr): 1613 (vs), 1465 (m), 1438 (w), 1422 (m), 1376 (m), 1329 (m), 1060 (vs), 864 (m),
748 (m), 691 (m) cm -1 .
1 H NMR (300 MHz, acetonitrile-d3): δ 1.40 (6H, s, CCH3) 1.45 (6H, s, CCH3), ABX spin
system (A = B = H, X = P) 3.54 (2H, 2 JAB = 18.3 Hz, 2 JPA = 16.0 Hz, PCHAHB), ABX spin
system (A = B = H, X = P) 4.35 (2H, 2 JAB = 18.3 Hz, 2 JPB = 14.2Hz, PCHAHB), AB spin
system 4.44 (2H, JAB = 8.9 Hz, OCHAHB), AB spin system 4.57 (2H, JAB = 8.9 Hz,
OCHAHB), 7.65 – 8.04 (5H, m, aromatic H); 13 C{ 1 H} NMR (75.5 MHz, acetonitrile-d3): δ
26.0 (s, C-CH3), 26.5 (s, C-CH3), 29.6 (d, 1 JPC = 41.8 Hz, PCH2), 68.4 (s, C(CH3)2), 83.4 (s,
OCH2), 121.7 (d, 1 JPC = 66.7 Hz, C-P of aryl), 130.1 (d, 2 JPC = 13.6 Hz, o-CH of aryl), 132.7
(d, 3 JPC = 12.0 Hz, m-CH of Aryl), 134.8 (d, 4 JPC = 3.3 Hz, p-CH of Aryl), 174.7 (d, 2 JPC =
19.8 Hz, C=N); 31 P{ 1 H} NMR (121.5 MHz, acetonitrile-d3): δ 43.92.
Anal. Calc. for C20H28B2F8N3O2PPd: C, 36.76; H, 4.32; N, 6.43. Found: C, 37.04; H, 4.56; N,
6.33.
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