Mixed Co–Ni carbide clusters. Part 1. Synthesis and structural characterization of the [Co3Ni9C(CO)20]3– trianion

Abstract

Reaction of [Co₃(CO)₉CCl] with [Ni₆(CO)₁₂]^2– results in a complicated mixture of mixed Co–Ni carbide carbonyl clusters, among which the [Co₃Ni₉C(CO)₂₀]^3– trianion has been isolated in a pure crystalline state and fully characterized by X-ray crystallography. The metal framework of this compound is unprecedented in cluster geometries and may be described as a square antiprism of metal atoms tetra-capped on two alternate pairs of adjacent triangular faces. Despite the presence of a caged carbon atom in the square-antiprismatic cavity, the compound is readily degraded by carbon monoxide (25 °C, 1 atm) mainly to a mixture of [Co(CO)₄]^– and [Ni(CO)₄]. Corresponding degradation of the cluster under a mixture of carbon monoxide and hydrogen yields, in addition, trace amounts of organics, mainly C₁ and C₂ hydrocarbons, probably derived from the carbide atom.