A mechanistic study of the c-p bond cleavage reaction of 1,2-(ph2)(2)-c6h4 with (buli)-bu-n/sb(nme2)(3)

Edge, R. and Less, R.J. and Naseri, V. and McInnes, E.J.L. and Mulvey, R.E. and Wright, D.S. (2008) A mechanistic study of the c-p bond cleavage reaction of 1,2-(ph2)(2)-c6h4 with (buli)-bu-n/sb(nme2)(3). Dalton Transactions (45). pp. 6454-6460. ISSN 1477-9234

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Abstract

In situ 31P NMR spectroscopic studies of the reaction of the primary diphosphine 1,2-(PH2)2-C6H4 with the mixed-metal base system nBuLi/Sb(NMe2)3, combined with X-ray structural investigations, strongly support a mechanism involving a series of deprotonation steps followed by antimony-mediated reductive C-P bond cleavage. The central intermediate in this reaction is the tetraphosphide dianion [C6H4P2]22- ([4]) from which the final products, the 1,2,3-triphospholide anion [C6H4P3]- (3) and [PhPHLi] (8·Li), are evolved. An EPR spectrocopic study suggests that homolytic C-P bond cleavage is likely to be involved in this final step.