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Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
Published on: October 3, 2014
Phosphine coordination complexes of the diphenylphosphenium cation: a versatile synthetic methodology for P-P bond
Neil Burford1, Paul J Ragogna, Robert McDonald
1Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, Canada, B3H 4J3. Neil.Burford@dal.ca
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.
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The reaction begins with the nucleophilic addition between a phosphorus ylide and the carbonyl compound. Due to its carbanionic character, phosphorus ylide acts as a strong nucleophile and attacks the electrophilic carbonyl group. This generates a charge-separated dipolar intermediate called betaine. The negatively charged oxygen atom and...

