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Oxidation, reduction, and copper-carbon bond formation in the reactions of copper(II) tetraglycine with pulse radiolytically generated free radicals

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic50207a053· OSTI ID:5183469

The reactions of copper(II) tetraglycine (Cu/sup II/G/sub 4/) with a variety of aliphatic free radicals and with .Br/sub 2//sup -/ and .OH have been investigated by the pulse radiolytic technique. Three types of reaction are observed: (i) oxidation of Cu/sup II/G/sub 4/ to Cu/sup III/G/sub 4/ by .Br/sub 2//sup -/ and .OH; (ii) rapid reduction to copper(I) by .CH/sub 2/OH, .CO/sub 2//sup -/, and (CH/sub 3/)/sub 2/COH; (iii) formation of unstable copper(III)-carbon-bonded intermediates with lifetimes from several milliseconds to several seconds with .CH/sub 2/C(CH/sub 3/)/sub 2/OH, .CH/sub 2/CO/sub 2//sup -/, and .CH/sub 2/C(OH)CH/sub 3/ radicals. Rate constants are reported for formation and decomposition of all intermediates, and the relative instability of neutral Cu/sup III/(H/sub -2/G/sub 4/) compared to Cu/sup III/(H/sub -3/G/sub 4/)/sup -/ is confirmed by direct observation.

OSTI ID:
5183469
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 19:5; ISSN INOCA
Country of Publication:
United States
Language:
English