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Phosphine and solvent effects on oxidative addition of CH3Br to Pd(PR3) and Pd(PR3)2 complexes

journal contribution
posted on 2023-05-17, 11:13 authored by Besora, M, Gourlaouen, C, Brian YatesBrian Yates, Maseras, F
The reaction between bromomethane CH3Br and Pd0 phosphine complexes Pd(PR3) and Pd(PR3)2 resulting in the corresponding PdII species Pd(PR3)(CH3)Br and Pd(PR3)2(CH3)Br was studied computationally with DFT methods. The oxidative addition can take place through two different mechanisms: concerted or SN2 transition state. The effect of a number of variables on the height of the barrier associated to each of these two mechanisms is systematically analyzed. The variables considered include the number of ligands on the metal (mono- or bis-phosphine), the nature of the phosphine (PF3,PH3, PMe3 or PPh3), and the nature of the solvent (gas phase, tetrahydrofuran or dimethylformamide). A number of trends can be identified, resulting in a complex picture where the nature of the phosphine and the solvent can be tuned to favor one of the two possible mechanisms, with the corresponding stereochemical implications that can be extrapolated to the behaviour of more sophisticated substrates.

History

Publication title

Dalton Transactions

Volume

40

Issue

42

Pagination

11089-11094

ISSN

1477-9226

Department/School

School of Natural Sciences

Publisher

Royal Society of Chemistry

Place of publication

Thomas Graham House, Science Park, Milton Rd, Cambridge, England, Cambs, Cb4 0Wf

Rights statement

Copyright 2011 The Royal Society of Chemistry

Repository Status

  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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