Synthesis and Carbonylation Studies on Methylpalladium(II) Complexes containing Chelating Pyridinecarboxylate Ligands: Dynamic Behaviour of the Ligands and Implications for the Carbonylation Mechanism

DOI: 10.1039/DT9950002159

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2159 - 2170 (1995)

Update date:2022-08-05

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Authors:

Jin, Hong

Cavell, Kingsley J.

Skelton, Brian W.

White, Allan H.

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Article abstract of DOI:10.1039/DT9950002159

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.

Full text of DOI:10.1039/DT9950002159

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