Synthesis and chemistry of diphenyl-2-pyridylphosphine complexes of palladium(0). X-Ray characterisation of Pd(Ph2Ppy)2(?2-DMAD) and trans-Pd(Ph2Ppy)2(PhC?CH2)(CF3CO2)

The zerovalent complexes Pd(Ph2Ppy)31 and Pd(Ph2Ppy)2(dba) 2, where Ph2Ppy is diphenyl-2-pyridylphosphine and dba = trans,trans-dibenzylideneacetone, have been synthesized and characterised. Reactions of 1 with alkynes have been studied and the dimethyl acetylenedicarboxylate complex Pd(Ph2Ppy)2(η2-DMAD) 3, where DMAD is dimethyl acetylenedicarboxylate, isolated and structurally characterised. The complexes trans-Pd(Ph2Ppy)2(PhC[double bond, length half m-dash]CH2)X, X = CF3CO2−4 or Cl−5, and trans-Pd(Ph2Ppy)2{CO(CH3)C[double bond, length half m-dash]CH2}Cl 6 result from oxidative addition of phenylacetylene/CF3CO2H, phenylacetylene/Et3NHCl and methacryloyl chloride respectively to 1, and the crystal structure of 4 is presented. The alkenyl ligand is bound to palladium through the α carbon in 4. Insertions into the M–C bond of the vinyl complexes have been studied. No isolable insertion product is obtained with carbon monoxide although the complex is active for the catalytic alkoxycarbonylation of phenylacetylene to 2-phenylpropenoate. Propadiene inserts into the Pd–C bond in 4 to give the cationic π-allyl complex [Pd(Ph2Ppy)2{η3-C3H4C(Ph)[double bond, length half m-dash]CH2}][CF3CO2] 7. The complex Pd(Ph2Ppy)3 is found to catalyse the vinylation of Ph2Ppy to the corresponding 2-propenylphosphonium trifluoromethanesulfonate