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)

Abstract

Reaction of tris(N,N-disubstituted dithiocarbamato)cobalt(III) complexes, [Co(S₂CNR₂)₃], with copper(I) halides, CuX, in acetonitrile deposits 1 : 3 and 2 : 5 adducts, [Co{S₂CN(CH₂)₄}₃]·3CuBr·MeCN (1) and 2[Co(S₂CNBuⁿ₂)₃]·5Cul (2), characterized by single-crystal structure determination and shown to contain novel CuX aggregates. In (1), [Co(S₂CNR₂)₂] molecules are linked by co-ordination of Cu₃Br₃oligomers in two of the three interligand ‘chelate’ sites to yield a one-dimensional polymer. The Cu₃Br₃unit is a six-membered ring in pseudo-‘boat’ conformation; two of the copper atoms are ‘chelated’ by [Co(S₂CNR₂)₃] molecules, while the third is three-co-ordinate with an acetonitrile appended. In (2), [Co(S₂CNR₂)₃] molecules are linked into a 1 : 1 dimer by chelated Cul₂Cu units; these units are further linked and cross-linked into a novel infinite double-stranded polymer by centrosymmetric Cu₆I₆, ‘displaced step’ units.