6
Tetrahedron
ACCEPTED MANUSCRIPT
13C{1H} NMR (75 MHz, 298 K, CDCl3) δ 157.3, 138.7 (d, J =
Tanaka, M., Eds. 2013; Vol. 43, p 145; e) Rosenberg, L.
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12.7 Hz), 132.8 (d, J = 18.3 Hz), 131.0 (d, J = 13.6 Hz), 129.6,
128.4 (d, J = 6.5 Hz), 127.4, 120.4, 110.2, 55.1, 28.4 (d, J = 12.1
Hz), 27.2 (d, J = 18.3 Hz); 31P{1H} NMR (121.5 MHz, 298 K,
CDCl3) δ −14.5; IR (solid) ν 3059, 2948, 2922, 2902, 2830,
1600, 1583, 1490, 1464, 1432, 852, 742, 696 cm-1; HRMS (EI)
[M + H]+ 321.1403 (calcd.), 321.1404 (obs.); m.p. 67 °C.
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2-(2-(Diphenylphosphanyl)ethyl)pyridine (3)
White solid, 1.17 g (84%). 1H NMR (300 MHz, 298 K,
CDCl3) δ 8.56 (d, 1H, J = 4.1 Hz), 7.62 - 7.43 (m, 5H), 7.43 -
7.29 (m, 6H), 7.20 - 7.03 (m, 2H), 3.05-2.82 (m, 2H), 2.64 - 2.48
(m, 2H); 13C{1H} NMR (75 MHz, 298 K, CDCl3) δ 161.9 (d, J =
13.3 Hz), 149.5, 138.5 (d, J = 13.0 Hz), 136.4, 132.9 (d, J = 18.6
Hz), 128.7, 128.6 (d, J = 6.8 Hz), 122.8, 121.3, 34.7 (d, J = 17.7
Hz), 28.1 (d, J = 12.4 Hz); 31P{1H} NMR (121.5 MHz, 298 K,
CDCl3) δ −14.6; IR (solid) ν 3046, 2920, 2949, 1590, 1567,
1470, 1479, 1433, 843, 781, 749, 735, 723, 697, cm-1; HRMS
(EI) [M + H]+ 292.1250 (calcd.), 292.1249 (obs.); m.p. 68-69 °C.
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Methyl 3-(diphenylphosphanyl)propanoate (4)
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1
Colourless oil, 1.00 g (80%). H NMR (300 MHz, 298 K,
CDCl3) δ 7.50 - 7.47 (m, 4H), 7.37 - 7.35 (m, 6H), 3.66 (s, 3H),
2.45 - 2.42 (m, 4H); 13C{1H} NMR (75 MHz, 298 K, CDCl3) δ
173.5 (d, J = 14.9 Hz), 137.7 (d, J =12.1 Hz), 132.7 (d, J = 18.3
Hz), 128.8, 128.5 (d, J = 6.5 Hz), 51.7, 30.5 (d, J = 19.3 Hz),
22.9 (d, J = 11.5 Hz); 31P{1H} NMR (121.5 MHz, 298 K, CDCl3)
δ −14.9; IR (solid) ν 3054, 2950, 1735, 1585, 1481, 1433, 1354,
848, 736, 694 cm-1; HRMS (EI) [M + H]+ 273.1039 (calcd.),
273.1040 (obs.)
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Complex 5
Isolated as yellow plates. Crystal data for for
C48H52Cl4O6P2Pd, 2(C1H2Cl2) (5, CCDC 1496173). M = 1035.03,
λ = 0.71073 Å, monoclinic, space group P1 21/c1, a =
11.6809(5), b = 24.1157(9), c = 8.9898(4)Å, α = 90, β =
110.174(5), γ = 90o, U = 2376.99(18) Å3, Z = 2, Dc = 1.446 g
cm-3, µ = 0.730 mm-1, F(000) = 1064. Crystal size = 0.516 ×
0.482 × 0.11 mm, unique reflections = 5441 [R(int) = 0.0324],
observed reflections [I>2σ(I)] = 4910, data/restraints/parameters
= 1064.0/0/279. Observed data; R1 = 0.0422, wR2 = 0.0814. All
data; R1 = 0.0490, wR2 = 0.0798. Max peak/hole = 0.439 and
−0.693 eÅ-3, respectively.
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Acknowledgements
We would like to thank the University of Bath and the EPSRC
for additional funding.
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References
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