Mechanism of oxidative dehydrogenation of alcohols co-ordinated to ruthenium
- 1 January 1992
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 12,p. 1949-1956
- https://doi.org/10.1039/dt9920001949
Abstract
The oxidative dehydrogenation of the complexes [Ru(bipy)2(NC5H4CH2OH)]2+, [Ru(bipy)2(NC5H4CD2OH)]2+ and [Ru(bipy)2{NC5H4CH(CH3)OH}]2+ to the corresponding carbonyl species [bipy = 2,2′-bipyridine; NC5H4CH2OH = 2-(hydroxymethyl)pyridine; NC5H4CD2OH = 2-(dideuteriohydroxymethyl)pyridine; NC5H4CH(CH3)OH = 2-(1-hydroxyethyl)pyridine] has been studied in aqueous solution by kinetic and electrochemical techniques. The mechanistic scheme was found to involve the intermediacy of a ruthenium(IV)–alkoxide species, formed by disproportionaton of the ruthenium(III) complex produced in the initial step of the oxidation process. The rate-determining removal of the proton from the α-carbon atom of the chelate ring is general-base catalysed.Keywords
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