Electron transfer. 157. Reactions of hypervalent manganese species with S(2) metal-ion reductants

Solutions of the complexes of hypervalent manganese, [Mn(III)(C(2)O(4))(3)](3)(-) (in oxalate buffers), [Mn(IV)(bigH)(3)](4+) (in biguanide buffers), and [(bipy)(2)Mn(III)(O)(2)Mn(IV)(bipy)(2)](3+) (in bipyridyl buffers) may be reduced by s(2) center reductants In(I), Sn(II), and Ge(II), yielding Mn(II) quantitatively. In all cases, rates are determined by the initial act of electron transfer, giving an s(1) transient (In(II), Sn(III), or Ge(III)); subsequent steps are rapid and kinetically silent. The In(I)-Mn(III) and Ge(II)-Mn(III) reactions are inhibited by added oxalate, whereas the Sn(II)-(Mn(III)Mn(IV)) reaction is strongly accelerated by Cl(-). The In(I)-Mn(IV) reaction is complicated by formation of a 1:1 addition compound In(I).Mn(IV). We find no evidence for two-unit steps in any of these systems.