A novel route to multinuclear d⁸ metal-chalcogen compounds with nuclearity control

We have designed a new synthetic procedure to obtain multinuclear aggregates containing a {Pt2S2}n core. The synthetic strategy involves the reaction of [(dppp)Pt(μ-S) 2Pt(dppp)] with [PtCl2(PhCN)2] and thus the expansion of the {Pt2S2} ring to a [{Pt2S 2}PtCl2] fragment. The lability of the chloride anions allows their replacement by bridging sulfide ligands, thus affording a new [{Pt2(μ3-S)2}{Pt2(μ-S) 2}{Pt2(μ3-S)2}] core. Its subsequent evolution to [{Pt2S2}3PtCl 2] lays the foundation for a new cycle. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.