Lewis base adducts of Group 11 metal(I) complexes. Part 48. Heterobimetallic tris(dithiocarbamato)cobalt(III)–copper(I) halide adducts as a vehicle for novel copper(I) halide clusters (structurally characterized)

Reaction of tris(N,N-disubstituted dithiocarbamato)cobaIt(tit) complexes, [Co(S,CNR,),], with copper(1) halides, CuX, in acetonitrile deposits 1 : 3 and 2: 5 adducts, [Co{S,CN(CH,),},]- 3CuBroMeCN (1 ) and 2[Co(S,CNBun,),]~5CuI ( Z ) , characterized by single-crystal strutcure determination and shown to contain novel CuX aggregates. In (1 ), [Co( S,CN R,),] molecules are linked by co-ordination of Cu,Br, oligomers in two of the three interligand 'chelate' sites to yield a one-dimensional polymer. The Cu,Br, unit is a six-membered ring in pseudo-'boat' conformation; two of the copper atoms are 'chelated' by [Co(S,CNR,),] molecules, while the third is three-coordinate with an acetonitrile appended. In ( Z ) , [Co(S,CNR,),] molecules are linked into a 1 : 1 dimer by chelated Cul,Cu units; these units are further linked and cross-linked into a novel infinite dou ble-stranded polymer by centrosymmetric CU,~, 'displaced step' units.Full Tex