Abstract
The reactivity of the two nickel complexes [Ni(xbsms)] and [Ni(bsms)~2~] [H~2~xbsms = α,α′‐bis(4‐mercapto‐3,3‐dimethyl‐2‐thiabutyl)‐o‐xylene; Hbsms = 4‐mercapto‐3,3‐dimethyl‐1‐phenyl‐2‐thiabutane] towards copper iodide and zinc bromide has been investigated. The reactions yield novel aggregates of higher nuclearity with topologies that are different from previous reports; the nickel complexes in all cases can be considered as didentate S ligands. The X‐ray structure of the novel octanuclear cluster [{Ni(bsms)~2~}~3~(CuI)~5~] shows a unique arrangement in which the cis‐NiS~2~S′~2~ units act as didentate ligands to a trigonal‐bipyramidal array of five Cu^I^ ions. The tetranuclear structure of [{Ni(xbsms)CuI}~2~] shows unprecedented asymmetric bridging of the thiolate sulfur atoms, with one of the thiolate groups binding to one copper ion and the other one μ~3~‐bridging to two copper ions. The complex is located on a crystallographic twofold axis and the complex in a single crystal is enantiomerically pure. The trinuclear complex [Ni~2~(bsms)~3~ZnBr~3~] is formed as a result of dissociation of the didentate bsms ligand from part of the mononuclear complex and reassembly to form a dinuclear core to which the ZnBr~3~^–^ unit is coordinated to a single thiolate sulfur atom. A complex of stoichiometry [Ni~3~(xbsms)~2~(ZnBr~3~)~2~] has also been isolated and a structure proposal based on spectroscopic properties is given. All complexes have been characterised by analytical and spectroscopic methods. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)