Role of bifunctional N/S bridging in the association of metals; syntheses and structures of heterobimetallic [(Ph(3)P)(2)CuL(2)Li(thf)(2)]center dot thf and tetrameric [{CuL(PPh(3))}(4)] (L=1,3-benzoxazoline-2-thionate, thf equals tetrahydrofuran)

Nucleophilic substitution of the cp (eta-C5H5) ligand of [Cu(cp)(PPh(3))] with LiL (L = 1,3-benzoxazoline-2-thionate) gave the heterobimetallic complex [(Ph(3)P)(2)CuL(2)Li(thf)(2)]. thf 1 (thf = tetrahydrofuran), the ligand-transfer reaction of which with CuCl2 generated the tetrameric cage complex [{CuL(PPh(3))}(4)] 2. The crystal structures of these complexes revealed that the association of the metal centres occurs by a variety of ligand co-ordination modes (mu-S, N; N, mu-S; mu(3)-S). Electrochemical measurements have been used to probe the nature of the species present in solution.