A New Route into Single-Crystalline Partially Oxidized Cobalt Compounds: Reactions with Zintl-Type Hexaselenodistannate(III) K6Sn2Se6 as Mild Oxidant

Abstract

Reactions of K6Sn2Se6 (1) with [Cp*CoCl]2 were investigated in order to probe the stability of the formal +3 oxidation state at Sn and possible ligand properties of heteroatomic zintl-type anion "Sn2Se6(6)- ". From these experiments, we obtained the following compounds that are oxidized to different extent as a result of the reaction with SnIII: [Cp2*Co][Cl2Co(mu2-Cl)2Li(thf)2] (2), [(Cp*Co)3(mu-Se)2] (3), [(Cp*Co)3(mu3-Se)2][Cl2Co(mu2-Cl)2Li(thf)2] (4), and [(Cp*Co)4(mu3-Se)4] (5). These compounds were structurally characterized by single-crystal X-ray diffractometry. It shows that the reaction conditions strongly affect the type and oxidation state of the isolated product. Two of the observed compounds, 3 and 4, are closely related both structurally and electronically; this is discussed and further illustrated by cyclovoltammetric measurements. The choice of the terminal Cp* ligand attached to the transition metal in the reactand complex is assumed to be basically dependent for the alignment of unexpected structural details when compared with known compounds of similar compositions. In conclusion, 1 is observed to act as mild oxidant as well as selenide donor, but is not in the position to keep its Sn-Se framework under the given reaction conditions.

Reactivity of Chalcogenostannate Compounds: Syntheses, Crystal Structures, and Electronic Properties of Novel Compounds Containing Discrete Ternary Anions [MII4(μ4-Se)(SnSe4)4]10- (MII = Zn, Mn)

“…In the course of studying the reactivity of chalcogenostannate anions, 16 (1). 19 1 contains the first known discrete ternary M/E′/E anion (E′ ) tetrel) besides those of the "pioneer" compounds.…”