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


Besora, M and Gourlaouen, C and Yates, B and Maseras, F, Phosphine and solvent effects on oxidative addition of CH3Br to Pd(PR3) and Pd(PR3)2 complexes, Dalton Transactions, 40, (42) pp. 11089-11094. ISSN 1477-9226 (2011) [Refereed Article]

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Copyright 2011 The Royal Society of Chemistry

DOI: doi:10.1039/C1DT10983A


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.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Organometallic chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Yates, B (Professor Brian Yates)
ID Code:76864
Year Published:2011
Web of Science® Times Cited:43
Deposited By:Chemistry
Deposited On:2012-03-14
Last Modified:2015-01-21

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