Jump to main content
Jump to site search

Issue 42, 2011
Previous Article Next Article

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

Author affiliations

Abstract

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.

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

Back to tab navigation

Supplementary files

Publication details

The article was received on 25 May 2011, accepted on 13 Jul 2011 and first published on 23 Aug 2011


Article type: Paper
DOI: 10.1039/C1DT10983A
Citation: Dalton Trans., 2011,40, 11089-11094
  •   Request permissions

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

    M. Besora, C. Gourlaouen, B. Yates and F. Maseras, Dalton Trans., 2011, 40, 11089
    DOI: 10.1039/C1DT10983A

Search articles by author

Spotlight

Advertisements