Synthesis and structural investigations of bulky imino- and amido-phosphine palladium dimers
Pascu, S. I., Anderson, G. D. W., Green, M. L. H., Green, J. C., Rees, N. H. and Cowley, A. R., 2006. Synthesis and structural investigations of bulky imino- and amido-phosphine palladium dimers. Inorganica Chimica Acta, 359 (11), pp. 3677-3692.
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The reactions of palladium(II) dimers [Pd2Br2(L1)(2)] and [Pd2Br2(L-2)(2)] (where L1(-) is [Ph2PCH=C(Ph)N(2,6-Pr2C6H3)](-) and L2(-) is [Ph2PCH=C(Ph)N(2,6-Me2C6H3)](-)) with AgBF4 in a mixture of CH2Cl2 and MeOH give palladium(I) dimers [Pd-2(HL1)(2)][BF4] and [Pd-2(HL2)(2)][BF4](2), respectively. These exhibit unusual coordination geometries of the metal centre. Density functional theory (DFT) and culations showed that a phenyl ring of the bridging phosphine is involved in bonding via a delocalised metal-phosphine-phenyl interaction. The remarkable kinetic stability of these palladium(l) species may explain the early termination steps in the CO/ethylene copolymerisation reaction catalysed by Pd(II)-amidophosphines or enolisable Pd(II)-iminophosphines.
|Creators||Pascu, S. I., Anderson, G. D. W., Green, M. L. H., Green, J. C., Rees, N. H. and Cowley, A. R.|
|Departments||Faculty of Science > Chemistry|
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