Palladium(II) complexes of new OPN phosphine ligands and their application in homogeneously catalysed reactions of CO with alkenes or alkynes

• Published in: Dalton transactions : an international journal of inorganic chemistry 2004-10 (20), p.3251-3260
• Main Authors: Green, Melinda J, Cavell, Kingsley J, Edwards, Peter G, Tooze, Robert P, Skelton, Brian W, White, Allan H
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/b405586c

Palladium complexes of a series of functionalised phosphines bearing the OPN donor set [2-pyCH(2)P(Ph)CH(2)(CHOCH(2)CH(2)CH(2)), 1; 2-py CH(2)P(Ph)-CH(2)CH(2)(CHOCH(2)CH(2)O), 2; 2-pyCH(2)P(Ph)CH(2)CH(2)CO(2)Me, 3; 2-pyP(Ph)CH(2)(CHOCH(2)CH(2)CH(2)), 4; 2-py = 2-pyridyl] have been prepared and characterised. Ligands 1-3 form five membered P-N chelates which is confirmed for PdCl(2) complexes of and by X-ray crystallography. O-coordination appears to be generally disfavoured although there is evidence of transient O-coordination for selected Pd complexes of 4. Palladium methyl and acetate complexes of all four ligands have been tested for catalytic activity in ethene/CO copolymerisation as well as alkoxy-carbonylation of propyne. Complexes of 1 and 4 show some activity in the copolymerisation reaction and complexes of 4 are active in the methoxy carbonylation of propyne. Unlike related pyridyl(diaryl)phosphines, 4 produces a much more stable catalyst system that does not require large excesses of ligand to maintain activity.