Issue 4, 2000

Synthesis and chemistry of diphenyl-2-pyridylphosphine complexes of palladium(0). X-Ray characterisation of Pd(Ph2Ppy)22-DMAD) and trans-Pd(Ph2Ppy)2(PhC[double bond, length half m-dash]CH2)(CF3CO2)

Abstract

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)22-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 = CF3CO24 or Cl5, 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)23-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.

Supplementary files

Article information

Article type
Paper
Submitted
06 Oct 1999
Accepted
17 Dec 1999
First published
27 Jan 2000

J. Chem. Soc., Dalton Trans., 2000, 523-528

Synthesis and chemistry of diphenyl-2-pyridylphosphine complexes of palladium(0). X-Ray characterisation of Pd(Ph2Ppy)22-DMAD) and trans-Pd(Ph2Ppy)2(PhC[double bond, length half m-dash]CH2)(CF3CO2)

A. Dervisi, P. G. Edwards, P. D. Newman and R. P. Tooze, J. Chem. Soc., Dalton Trans., 2000, 523 DOI: 10.1039/A908050C

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