Phosphine coordination complexes of the diphenylphosphenium cation: a versatile synthetic methodology for P-P bond formation

Neil Burford; Paul J Ragogna; Robert McDonald; Michael J Ferguson

doi:10.1021/ja036649w

Phosphine coordination complexes of the diphenylphosphenium cation: a versatile synthetic methodology for P-P bond formation

J Am Chem Soc. 2003 Nov 26;125(47):14404-10. doi: 10.1021/ja036649w.

Authors

Neil Burford¹, Paul J Ragogna, Robert McDonald, Michael J Ferguson

Affiliation

¹ Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, Canada, B3H 4J3. Neil.Burford@dal.ca

PMID: 14624588
DOI: 10.1021/ja036649w

Abstract

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.