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Issue 13, 2009
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Electronic effects in oxo transfer reactions catalysed by salan molybdenum(VI) cis-dioxo complexes

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Abstract

A series of molybdenum(VI) cis-dioxo complexes containing tetradentate salan ligands with different para-substitutions on the phenoxy group have been prepared. These complexes catalyse the oxygen atom transfer reaction between dimethylsulfoxide and triphenylphosphine. During oxo transfer catalysis, the complexes are resistant to formation of catalytically inactive oxo-bridged dimeric Mo(V) complexes. Electronic effects influence the rate of the oxo transfer reaction and the fastest rates are achieved when the para-phenoxy substituent is an electron withdrawing nitro substituent. Hammett correlations have shown that the rate-determining step involves nucleophillic attack of the phosphine on one of the oxo ligands. Electrochemical measurements have shown that all complexes containing tertiary amine ligands exhibit quasi-reversible behaviour and that the para-substituent has a considerable effect on the half potentials (E1/2). A linear correlation between the E1/2 values and the Hammett σp parameter is observed.

Graphical abstract: Electronic effects in oxo transfer reactions catalysed by salan molybdenum(vi) cis-dioxo complexes

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Publication details

The article was received on 21 Nov 2008, accepted on 09 Jan 2009 and first published on 17 Feb 2009


Article type: Paper
DOI: 10.1039/B820754B
Citation: Dalton Trans., 2009, 2337-2344
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    Electronic effects in oxo transfer reactions catalysed by salan molybdenum(VI) cis-dioxo complexes

    C. J. Whiteoak, G. J. P. Britovsek, V. C. Gibson and A. J. P. White, Dalton Trans., 2009, 2337
    DOI: 10.1039/B820754B

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