Reactions of octacyanomolybdate(v) and octacyanotungstate(v) with s2 metal-ion reducing centers

Abstract

The s² centers, Sn(II), Ge(II), and In(I) reduce Mo^V(CN)₈³⁻ and W^V(CN)₈³⁻ quantitatively to the corresponding octacyanomolybdate(IV) and -tungstate(IV) anions. Reductions by In(I) proceed 10³–10⁵ times as rapidly as those by Sn(II) and Ge(II). All reactions are triggered by a single electron oxidation, yielding a much more reactive s¹ intermediate. Reductions by Sn(II) in chloride medium proceed predominantly through the SnCl₃⁻ anion. The Ge(II)–W(CN)₈³⁻ reaction is initiated by a slow unimolecular heterolysis of the Ge(II) center, yielding very nearly linear profiles when the reductant is in excess.