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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, FThe 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 TransactionsVolume
40Issue
42Pagination
11089-11094ISSN
1477-9226Department/School
School of Natural SciencesPublisher
Royal Society of ChemistryPlace of publication
Thomas Graham House, Science Park, Milton Rd, Cambridge, England, Cambs, Cb4 0WfRights statement
Copyright 2011 The Royal Society of ChemistryRepository Status
- Restricted