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

✍ Scribed by Cristina Femoni; Maria Carmela Iapalucci; Giuliano Longoni; Fabrizio Ranuzzi; Stefano Zacchini; Serena Fedi; Piero Zanello

• Publisher: John Wiley and Sons
• Year: 2007
• Tongue: English
• Weight: 180 KB
• Volume: 2007
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200700159

✦ Synopsis

Abstract

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)