Condensation of Nickel–Carbonyl Clusters with Soft Lewis Acids: Synthesis and Characterisation of the {Cd 2 Cl 3 [Ni 6 (CO) 12 ] 2 } 3– Dimer

Reaction of [Ni 6 (CO) 12 ] 2– in thf with 2 equiv. of the softLewis acid CdCl 2 ·2.5H 2 O gives the new dimeric species {Cd 2 Cl 3 [Ni 6 (CO) 12 ] 2 } 3– . The formation of the latter is not the result of direct addition of CdCl 2 to [Ni 6 (CO) 12 ] 2– , but it involves some intermediate species, i.e. [Ni 9 (CO) 18 ] 2– and [Ni 9 (CO) 18 Cd 2 Cl 4 ] 2– . The crystal structure of [NBu 4 ] 3 {Cd 2 Cl 3 [Ni 6 (CO) 12 ] 2 }·thf was ascertained by X‐ray crystallography. In the solid state, the {Cd 2 Cl 3 [Ni 6 (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 {Cd 2 Cl 3 [Ni 6 (CO) 12 ] 2 } 3– are also reported and compared to those of the parent [Ni 6 (CO) 12 ] 2– dianion.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)