Trivalent Copper. II. A Pulse Radiolytic Study of the Formation and Decomposition of Amino Complexes

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Abstract

The effect of amino ligands on the radiolytic induced formation and decomposition of trivalent copper complexes was studied. The spectra of the Cu(III) complexes with ammonia, ethylenediamine, and different amino acids weee measured. The specific rates of oxidation of Cu(NH3)42+ by. NH2 radicals and the complexes of Cu2+ with ethylenediamine and different amino acids by -OH radicals were determined. The CuIII(NH3)n complex decomposes via a second-order reaction. The CuIII(en)2 complex also decomposes via a second-order reaction. The specific rate of the latter reaction increases with increasing pH from 2k = 5.5×105 M-1 sec-1 at pH 5.8 to 2k = 3.9 × 107 M-1 sec-1 at pH 11.6. It is suggested that this increase is due to the formation of. OH radicals as an intermediate in the decomposition reaction in alkaline solutions. All the amino acid complexes of Cu(III) decompose via a first-order reaction with a specific rate of (1-8)×103 sec-1. It is suggested that the first step in the latter reaction is an intramolecular electron transfer from the carboxylic group to the central copper atom. The specific rate of the reaction Cu(III)aq + CuIIgly→Cuaq2+ + CuIIIgly was measured: k = 8.1 × 107 M-1 sec-1.

Original languageEnglish
Pages (from-to)2244-2249
Number of pages6
JournalInorganic Chemistry
Volume10
Issue number10
DOIs
StatePublished - 1 Oct 1971
Externally publishedYes

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