Redox–chemical core manipulation of [Os18Hg3C2(CO)42]2–; synthesis and crystal structure of the cluster [Os18Hg2C2(CO)42]4–

Abstract

The extrusion of metallic mercury from [Os₁₈Hg₃C₂(CO)₄₂]^2–1 by reduction has been studied and the tetraanionic cluster [Os₁₈Hg₂C₂(CO)₄₂]^4–3 isolated and characterised. The structure of the [N(PPh₃)₂]⁺ salt of 3 has been established by a single-crystal X-ray structure analysis. Oxidation of 3 with [Fe(η⁵-C₅H₅)₂]BF₄ yielded the corresponding tri- and di-anionic clusters 4 and 2. The clusters 1–4 were found to be interrelated by reversible photochemical and redox–chemical transformations. This reactive behaviour is reflected in the results of an electrochemical study of 1 by cyclic voltammetry.