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

Michael Lesslie; Yang Yang; Allan J. Canty; Elettra Piacentino; Francis Berthias; Philippe Maitre; Victor Ryzhov; Richard A. J. O'Hair

doi:10.1039/C7CC08944A

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

Michael Lesslie,^a Yang Yang,^b Allan J. Canty,

^c Elettra Piacentino,^a Francis Berthias,^d Philippe Maitre,

^d Victor Ryzhov

*^a and Richard A. J. O'Hair

*^b

Author affiliations

* Corresponding authors

^a Department of Chemistry and Biochemistry, and Center for Biochemical and Biophysical Sciences, Northern Illinois University, DeKalb, IL 60115, USA
E-mail: ryzhov@niu.edu

^b School of Chemistry, Bio21 Institute of Molecular Science and Biotechnology, The University of Melbourne, Victoria 3010, Australia
E-mail: rohair@unimelb.edu.au

^c School of Physical Sciences, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia

^d Laboratoire de Chimie Physique, Bâtiment 349, Université Paris-Sud, CNRS, Université Paris-Saclay, France

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.

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DOI: https://doi.org/10.1039/C7CC08944A
Article type: Communication
Submitted: 21 Nov 2017
Accepted: 05 Dec 2017
First published: 11 Dec 2017
This article is Open Access

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Chem. Commun., 2018,54, 346-349

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

M. Lesslie, Y. Yang, A. J. Canty, E. Piacentino, F. Berthias, P. Maitre, V. Ryzhov and R. A. J. O'Hair, Chem. Commun., 2018, 54, 346 DOI: 10.1039/C7CC08944A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Chemical Communications

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

Abstract

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Article information

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

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