Inorganic Chemistry, Vol.39, No.6, 1200-1203, 2000
Electron transfer. 141. Reactions of indium(I) with transition metal center oxidants
Aqueous solutions of the hypovalent state In(I) reduce a series of complexes of Fe(III) and selected derivatives of Ir(IV), Cr(V), Pt(IV), Ag(III), and Ni(IV). All reactions yield In(III). Ions derived from Fe(III) and Ir(IV) undergo net le(-) conversions, whereas the other oxidants change by two units. Reductions of Fe(III) are strongly promoted by increasing pH or by adding Cl-, Br-, NCS-, or N-3(-). Reaction appears to proceed through monoligated complexes, Fe-III(Lig(-))(2+), and the kinetic response to alteration of added ligand indicates initiation mainly via a bridged transition state Fe-III-Lig-In-I. Oxidations by Fe(CN)(6)(3-) are exceptionally rapid, those by Fe-III(EDTA) are unusually slow, and redox is blocked by addition of excess F-. Reduction of IrCl62- proceeds somewhat more slowly than predicted by the Marcus model for outer-sphere reactions, Conversions of the 2e(-) oxidants are rapid. For these, multistep routes initiated by le- changes are reasonable, but direct 2e(-) paths involving oxygen transfer (from (CrO)-O-V) or Cl+ transfer (from PtCl62-) cannot be ruled out. Whether inner-sphere 2e(-) transactions without transfer of atomic species can be competitive remains an open question.