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Phosphine Coordination Complexes of the Diphenylphosphenium Cation:  A Versatile Synthetic Methodology for P−P Bond Formation

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posted on 2003-11-26, 00:00 authored by Neil Burford, Paul J. Ragogna, Robert McDonald, Michael J. Ferguson
A series of phosphine−diphenylphosphenium donor−acceptor cationic complexes have been synthesized and comprehensively characterized (phosphine = diphenylchlorophosphine, triphenylphosphine, trimethylphosphine, and tricyclohexylphosphine). The complexes involve homoatomic P−P coordinate bonds that are susceptible to ligand exchange reactions highlighting a versatile new synthetic method for P−P bond formation. Phosphenium complexes of 1,2-bis(diphenylphosphino)benzene and 1,2-bis(tert-butylphosphino)benzene undergo unusual rearrangements to give a “segregated” diphosphine−phosphonium cation and a cyclic di(phosphino)phosphonium cation, respectively. The rearrangement products reveal the kinetic stability of the phosphine−phosphenium bonding arrangement.

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