Constructing Multimetallic Systems with the Naphthalene‐1,8‐bis(thiolato) Ligand

Addition of 1 equiv. (Ph3P)Au(ClO4) (formed by ion exchange of Ph3PAuCl with AgClO4) to [naphthalene‐1,8‐bis(thiolato)]bis(triphenylphosphane)platinum results in the formation of a novel dimetallic cationic complex with a (triphenylphosphane)gold moiety attached to the sulfur of the naphthalene‐1,8‐bis(thiolato) ligand. NMR spectroscopic evidence suggests that this gold‐containing fragment is fluxional in its bonding and X‐ray crystallography confirms the asymmetric complex, which shows this gold atom attached to one of these sulfur atoms. Addition of more than 1 equiv. (Ph3P)Au(ClO4) results in the formation of a tetrametallic sandwich complex with two bridging gold atoms between the sulfur atoms of the two PtS2C3 rings. Tri‐ and tetrametallic silver‐containing complexes can be prepared by addition of 0.5 and 1 equiv. AgClO4 to (Ph3P)2Pt(S2C10H6), respectively. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)