Mechanism of oxidative dehydrogenation of an amine coordinated to osmium(II)

Keene, F. Richard, Lay, Peter A., Sneddon, Graeme E., and Whebell, Geoffrey W. (1993) Mechanism of oxidative dehydrogenation of an amine coordinated to osmium(II). Australian Journal of Chemistry, 46 (11). pp. 1763-1774.

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The synthesis and characterization of [Os(bpy)₂(ampy)]²⁺{bpy = 2,2'-bipyridine; ampy = 2-(aminomethyl)pyridine} have been studied, together with its irreversible two-electron oxidative dehydrogenation to the corresponding osmium(II) imine species in aqueous solution, by utilizing electrochemical and stopped-flow kinetic techniques. The kinetic data were analysed by using numerical integration methods to obtain solutions for the differential equations derived from mechanistic proposals. The results were consistent with the initial oxidation of the metal centre to Os(III) and the intermediacy of a deprotonated Os(IV) species, formed by disproportionation, in the subsequent ligand dehydrogenation.

Item ID: 22781
Item Type: Article (Research - C1)
ISSN: 1445-0038
Keywords: macrocyclic complexes; aqueous-solutions; pulse-radiolysis; ruthenium; kinetics; redox; disproportionation; reactivity; ligand; atom
Date Deposited: 16 Aug 2012 02:31
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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