The chemical mechanism for electron transfer and bridge reducibility

William L. Purcell

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

One limiting mechanism proposed for bridged inner-sphere, electron transfer reactions, the chemical mechanism, involves rate-limiting reduction of the bridge to a radical by the reducing centre followed by rapid reduction of the oxidizing centre by the radical bridge. One predicted kinetic trait of such reactions is a correlation between the electron transfer rate constant and the "reducibility" of the bridge. This predicted trend is quantified here for the first time, with bridge reducibility expressed in terms of adiabatic gas-phase electron affinities. Also, a new kinetic test to distinguish outer-sphere electron transfers from those proceeding the chemical mechanism is shown to develop from the dependence of the rate constant on electron affinity.

Original languageEnglish
Pages (from-to)563-565
Number of pages3
JournalPolyhedron
Volume8
Issue number4
DOIs
StatePublished - Jan 1 1989

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electron transfer
Electrons
Electron affinity
electron affinity
Rate constants
Kinetics
kinetics
Gases
vapor phases
trends

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

The chemical mechanism for electron transfer and bridge reducibility. / Purcell, William L.

In: Polyhedron, Vol. 8, No. 4, 01.01.1989, p. 563-565.

Research output: Contribution to journalArticle

Purcell, William L. / The chemical mechanism for electron transfer and bridge reducibility. In: Polyhedron. 1989 ; Vol. 8, No. 4. pp. 563-565.
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