Ligand-induced decarbonylation in diphosphine-ligated palladium acetates [CH3CO2Pd((PR2)2CH2)] (R = Me and Ph)

M Lesslie; Y Yang; AJ Canty; E Piacentino; F Berthias; P Maitre; V Ryzhov; RAJ O'Hair

Journal article

Ligand-induced decarbonylation in diphosphine-ligated palladium acetates [CH3CO2Pd((PR2)2CH2)] (R = Me and Ph)

M Lesslie, Y Yang, AJ Canty, E Piacentino, F Berthias, P Maitre, V Ryzhov, RAJ O'Hair

Chemical Communications | ROYAL SOC CHEMISTRY | Published : 2018

DOI: 10.1039/c7cc08944a

Abstract

A new decarbonylation reaction is observed for [(K2-acetate)Pd(K2-diphosphine)]+ complexes. Gas-phase IR experiments identify the product as [CH3Pd(OP(Ph2)CH2PPh2)]+. DFT calculations uncovered a plausible mechanism involving O atom abstraction by the diphosphine ligand within the coordination sphere to yield the acetyl complex, [CH3COPd(OP(Ph2)CH2PPh2)]+, which then undergoes decarbonylation.

University of Melbourne Researchers

Richard O'Hair Author

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Grants

Awarded by University of Melbourne

Funding Acknowledgements

We acknowledge support from the Australian Research Council (DP150101388) and the National Computing Infrastructure. Financial support from European Community's Framework Programme Horizon 2020 (CALIPSOplus, under grant agreement 730872) is gratefully acknowledged. ML thanks NIU graduate student travel award for funding his trip to conduct research at the University of Melbourne. We thank Victor Wan for carrying out preliminary DFT calculations.