Issue 43, 2019

The diverse mechanisms for the oxidative addition of C–Br bonds to Pd(PR3) and Pd(PR3)2 complexes

Abstract

The reaction between bromobenzene and palladium(0) complexes leading to a palladium(II) complex containing bromide and phenyl ligands is studied computationally with DFT methods. Three different mechanisms are considered: concerted, nucleophilic substitution and radical. A systematic analysis is carried out on the effect on each of these mechanisms of a number of variables: the identity of the phosphine (PF3, PH3, PMe3 or PPh3), the nature of the solvent (vacuum, tetrahydrofuran, dimethylformamide or water) and the number of phosphine ligands (mono- or bis-phosphine). The concerted and nucleophilic substitution mechanisms are competitive in many cases, the identity of the preferred one depending on a combination of factors. Additional calculations with bromomethane, bromoethylene and bromoethane are carried out in selected cases for further clarification.

Graphical abstract: The diverse mechanisms for the oxidative addition of C–Br bonds to Pd(PR3) and Pd(PR3)2 complexes

Supplementary files

Article information

Article type
Paper
Submitted
02 août 2019
Accepted
03 oct. 2019
First published
03 oct. 2019

Dalton Trans., 2019,48, 16242-16248

The diverse mechanisms for the oxidative addition of C–Br bonds to Pd(PR3) and Pd(PR3)2 complexes

M. Besora and F. Maseras, Dalton Trans., 2019, 48, 16242 DOI: 10.1039/C9DT03155C

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