Electron Transfer. 130. Reductions with Indium(I)(1) |
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Authors: | Chandra Swapan K Gould Edwin S |
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Institution: | Department of Chemistry, Kent State University, Kent, Ohio 44242. |
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Abstract: | Aqueous solutions of the hypovalent state indium(I) have been prepared by treatment of In(Hg) with silver triflate in acetonitrile, followed by dilution with oxygen-free water. These solutions are stable for over 5 h at 25 degrees C. In(I)(aq) reacts with oxidants of the type (NH(3))(5)Co(III)(Lig)](2+) (In(I) + 2Co(III) --> In(III) + 2Co(II)), and kinetic profiles are consistent with a two-step sequence proceeding with formation of the metastable state In(II), which reacts rapidly with Co(III). Rate ratios for reductions of halogeno-substituted oxidants point to predominance of halide-bridged paths for the chloro, bromo and iodo complexes. Reductions of carboxylato-substituted derivatives are slow but appear to entail inner-sphere precursors if aided by an O-donor group in a position favorable for chelation. In no case is there evidence for reaction via initial reduction of the ligand (the radical-cation mechanism) although the potential of the In(I,II) couple (-0.40 V) allows this path for carbonyl-substituted oxidants. Reductions by In(I), like those by Eu(II), make no significant use of bridging by heterocyclic donor nitrogen centers in pyridine and pyrazine complexes. |
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