Issue 0, 1968

The kinetics of the decomposition of amido- and superoxo-bridged binuclear complexes of cobalt

Abstract

The kinetics of the decomposition of the single-bridged decammine µ-amido- and µ-superoxo-dicobalt complexes (NH3)5Co·NH2·Co(NH3)55+ [graphic omitted] Co(NH3)63++ Co(NH3)5H2O3+, and (NH3)5Co·O2·Co(NH3)55+ [graphic omitted] Co(NH3)5H2O3++ Co2++ 5NH4++ O2, have been studied in aqueous perchloric acid, µ= 2·0M, in the range 47·3–80°. Both reactions are first-order in complex and independent of hydrogen-ion concentration in the range 0·02–2·0M. At 64·6°k1= 13·5 × 10–5 sec.–1 and k2= 6·65 × 10–5 sec.–1; the activation parameters are ΔH1= 31·5 ± 1·2 kcal. mole–1, ΔS1= 5·6 ± 3 e.u., ΔH2= 28·1 ± 1·2 kcal, mole–1, and ΔS2= 17 ± 3·5 e.u. respectively.

In the decomposition of the double-bridged complex (NH3)4Co·µ(NH2,O2)·Co(NH3)44+ at 85° and µ= 2·0M, the rate constant for the disappearance of complex is ca. 4·1 × 10–5 sec.–1. Evidence for the formation of a single-bridged intermediate is considered.

Article information

Article type
Paper

J. Chem. Soc. A, 1968, 1031-1034

The kinetics of the decomposition of amido- and superoxo-bridged binuclear complexes of cobalt

R. D. Mast and A. G. Sykes, J. Chem. Soc. A, 1968, 1031 DOI: 10.1039/J19680001031

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements