Issue 5, 1985

Electron-transfer reactions from cis-dialkylbis(2,2′-bipyridyl)cobalt(III) complexes to organic oxidants

Abstract

One-electron oxidation of cis-[CoR2(bipy)2]ClO4(R = Me or Et; bipy = 2,2′-bipyridine) by organic oxidants (2,3-dichloro-5,6-dicyano-p-benzoquinone, 2,3-dicyano-p-benzoquinone, tetracyanoethylene, and tetracyano-p-quinodimethane) in acetonitrile results in the cleavage of the pair of cobalt–alkyl bonds to yield the coupled products (R–R) exclusively. A transient absorption band observed in the electron-transfer reaction of [CoEt2(bipy)2]+ with tetracyanoethylene is shown to arise from a charge-transfer complex formed between [CoEt2(bipy)2]+ and tetracyanoethylene as a reaction intermediate. The logarithm of the rate constants (log k) for these electron-transfer reactions in acetonitrile at 298 K is linearly correlated with the difference in the redox potentials between [CoR2(bipy)2]+ and oxidants with a slope of –F/2.3RT(F is the Faraday constant). Based on the linear Gibbs energy relationship, mechanisms for the electron-transfer reactions are discussed with the aid of the Marcus theory, and the lifetimes of cis-[CoR2(bipy)2]2+ are estimated as ⩽8 × 102 ns.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1985, 899-904

Electron-transfer reactions from cis-dialkylbis(2,2′-bipyridyl)cobalt(III) complexes to organic oxidants

S. Fukuzumi, K. Ishikawa and T. Tanaka, J. Chem. Soc., Dalton Trans., 1985, 899 DOI: 10.1039/DT9850000899

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