Reactivity of Hydrogen Atoms toward Some Cobalt (III) Complexes in Aqueous Solutions

Jack Halpern, Joseph Rabani

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24 Scopus citations

Abstract

Kinetic studies on the reduction of various cobalt(III) complexes by hydrogen atoms are described. The hydrogen atoms were generated by Co60 γ irradiation of the solutions and the rates of reaction with thecobalt(III) complexes determined by competition with the reaction with ethanol. Rate constants ranging from 3.3 X 1010 to 2.0 X 107 M-1 sec-1 (at 26°) were determined for the reactions of H atoms with Co(NH3)5I2+, Co(NH3)5Br2+, Co-(NH3)5NCS2+, Co(NH3)5(H-fumarate)2+, Co(NH3)5Cl2+, Co(NH3)5N32+, Co(NH3)3(N02)3, Co(NH3)5N022+, Co-(NH3)5CN2+, and Co(CN)63-, along with upper limits for reactions with a number of other cobalt(III) complexes. In a number of cases the rates of reactions with the corresponding free ligands also were determined. The mechanisms of these reactions and the relation of the observed reactivity patterns for H atoms to those for other reductants are considered.

Original languageEnglish
Pages (from-to)699-704
Number of pages6
JournalJournal of the American Chemical Society
Volume88
Issue number4
DOIs
StatePublished - Feb 1966
Externally publishedYes

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