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(S 2 CNR 2) 3 ], with copper(I) halides, CuX, in acetonitrile deposits 1:3 and 2:5 adducts, [Co{S 2 CN(CH 2) 4 } 3 ]·3CuBr·MeCN (1) and 2[Co(S 2 CNBu n 2) 3 ]·5Cul (2), characterized by single-crystal structure determination and shown to contain novel CuX aggregates. In (1), [Co(S 2 CNR 2) 2 ] molecules are linked by co-ordination of Cu 3 Br 3 oligomers in two of the three interligand 'chelate' sites to yield a one-dimensional polymer. The Cu 3 Br 3 unit is a six-membered ring in pseudo-'boat' conformation; two of the copper atoms are 'chelated' by [Co(S 2 CNR 2) 3 ] molecules, while the third is three-co-ordinate with an acetonitrile appended. In (2), [Co(S 2 CNR 2) 3 ] molecules are linked into a 1:1 dimer by chelated Cul 2 Cu units; these units are further linked and cross-linked into a novel infinite double-stranded polymer by centrosymmetric Cu 6 I 6, 'displaced step' units.