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Electron Transfer. 130. Reductions with Indium(I)(1).

Swapan K. Chandra1, Edwin S. Gould

  • 1Department of Chemistry, Kent State University, Kent, Ohio 44242.

Inorganic Chemistry
|June 19, 1996
PubMed
Summary

Stable aqueous solutions of indium(I) were prepared and studied. Indium(I) reacts with cobalt(III) oxidants via a two-step process, forming indium(II) and yielding indium(III).

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Area of Science:

  • Inorganic Chemistry
  • Solution Chemistry
  • Redox Reactions

Background:

  • Hypohalite species like indium(I) are challenging to stabilize in aqueous solutions.
  • Understanding the redox behavior of indium(I) is crucial for its potential applications.

Purpose of the Study:

  • To prepare and characterize stable aqueous solutions of indium(I).
  • To investigate the reaction kinetics and mechanisms of indium(I) with various cobalt(III) oxidants.

Main Methods:

  • Preparation of indium(I) solutions using In(Hg) and silver triflate in acetonitrile, followed by dilution with deoxygenated water.
  • Kinetic studies of indium(I) reactions with [(NH3)5Co(III)(Lig)]2+ oxidants, varying the ligand (L).
  • Analysis of reaction rates and product distributions to elucidate reaction mechanisms.

Main Results:

  • Stable aqueous indium(I) solutions were obtained, persisting for over 5 hours at 25°C.
  • Indium(I) reacts with cobalt(III) oxidants in a two-step process involving a metastable indium(II) intermediate.
  • Halide-bridged pathways dominate for chloro, bromo, and iodo cobalt(III) complexes, while carboxylato complexes show slow reactions possibly involving inner-sphere precursors.
  • No evidence for ligand radical-cation mechanisms was observed, despite the electrochemical potential allowing for it.

Conclusions:

  • Aqueous indium(I) is a viable and stable reducing agent.
  • The reaction mechanism with cobalt(III) oxidants is primarily outer-sphere, with specific pathways dictated by the oxidant's ligand.
  • Indium(I) reduction pathways do not significantly involve bridging through heterocyclic nitrogen atoms.

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