Condensation of Nickel–Carbonyl Clusters with Soft Lewis Acids: Synthesis and Characterisation of the {Cd2Cl3[Ni6(CO)12]2}3– Dimer

Abstract

AbstractReaction of [Ni6(CO)12]2– in thf with 2 equiv. of the softLewis acid CdCl2·2.5H2O gives the new dimeric species {Cd2Cl3[Ni6(CO)12]2}3–. The formation of the latter is not the result of direct addition of CdCl2 to [Ni6(CO)12]2–, but it involves some intermediate species, i.e. [Ni9(CO)18]2– and [Ni9(CO)18Cd2Cl4]2–. The crystal structure of [NBu4]3{Cd2Cl3[Ni6(CO)12]2}·thf was ascertained by X‐ray crystallography. In the solid state, the {Cd2Cl3[Ni6(CO)12]2}3– cluster anions are pillared along the crystallographic c axis, forming infinite columns of perfectly alternating cluster anions and thf molecules. The chemical and electrochemical behaviours of {Cd2Cl3[Ni6(CO)12]2}3– are also reported and compared to those of the parent [Ni6(CO)12]2– dianion.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)