168413-19-2Relevant articles and documents
Synthesis and Carbonylation Studies on Methylpalladium(II) Complexes containing Chelating Pyridinecarboxylate Ligands: Dynamic Behaviour of the Ligands and Implications for the Carbonylation Mechanism
Jin, Hong,Cavell, Kingsley J.,Skelton, Brian W.,White, Allan H.
, p. 2159 - 2170 (2007/10/03)
Methylpalladium complexes of the general formula were synthesised and the dynamic behaviour of the ligands pyca and L studied in detail.The ligands were found to undergo readily a variety of exchange reactions, clearly demonstrating their lability under mild conditions.The ligand exchange behaviour and data on rates of carbonylation for the palladium complexes led to a dissociative mechanism, requiring lability in both the ligand L and the chelate, being proposed for the CO insertion process.The methylpalladium complexes exist in solution as a mixture of cis and trans isomers.However the acyl complexes were found to occur only in the geometry with the phosphine cis to the acyl group.X-Ray crystal structures were obtained for the complexes > and .The complexes have distorted square-planar geometry: for the palladium complex, which is highly distorted, P-Pd-O(21) 97.3(1), P-Pd-C(01) 88.9(2), N-Pd-O(21) 78.4(2) and N-Pd-C(01) 95.9(2) deg and for the platinum complex P-Pt-O(21) 93.9(5), P-Pt-C(01) 95.1(9), N-Pt-O(21) 80.4(7) and N-Pt-C(01) 91(1) deg.