Embryonic brass: pseudo two electron Cu/Zn clusters

Abstract

The isoelectronic M₇ clusters [Cu₃Zn₄](Cp*)₅ (1) and {[Cu₂Zn₅](Cp*)₅}⁺ (2) are described. While 1 can be isolated only as a minor side product from the reaction of Cu(CH₃CO₂) with equimolar amounts of [Zn₂Cp*₂] with the trigonal cluster [CuZn₂](Cp*)₃ as the major product, 2 is available in acceptable yields from the reaction of [CuZn₂](Cp*)₃ with the Cp*Zn₂-transfer-reagent [Cp*Zn₂(Et₂O)₃][BAr₄^F]. The trigonal bipyramidal Cu/Zn-clusters exhibit exceptional bonding situations: with formally only one skeleton electron pair they can be regarded as highly electron deficient. However, a detailed DFT analysis reveals that the cluster bonding is supported by 3d orbital contributions of the trigonal metal base unit. The data contribute to the development of an advanced tool-box for synthesis of Hume-Rothery intermetallic (e.g. brass) inspired clusters.