Abstract
The outstanding nucleophilicity of the {Pt(μ‐S)~2~Pt} core in compounds [L~2~Pt(μ‐S)~2~PtL~2~] (L~2~ = phosphane) accounts for their ability to act as metalloligands towards main group and transition metals, and thus for the high number of [{L~2~Pt(μ~3~‐S)~2~PtL~2~}~x~ML′~y~]^z^ aggregates already described. However, the electronic and molecular features underpinning this behavior anticipate a landscape of comparable richness for the reactions of [L~2~Pt(μ‐S)~2~PtL~2~] with non‐metal electrophiles. Exploration of the chemistry of [L~2~Pt(μ‐S)~2~PtL~2~] (L~2~ = chelating diphosphane) towards various electron‐acceptor species has been the aim of our research for the past years. In this microreview we survey the synthetic strategies of [L~2~Pt(μ‐S)~2~PtL~2~] compounds, their distinguishing electronic and molecular features, the dynamic processes and electron‐donor properties of the {Pt(μ‐S)~2~Pt} core, and its binding ability towards metal centers. Moreover, particular attention is given to the reaction chemistry of [L~2~Pt(μ‐S)~2~PtL~2~] with organic electrophiles and protic acids, as well as to the influence of the {Pt(μ‐S)~2~Pt} core on the reactivity of inorganic or organic L′ ligands in [{L~2~Pt(μ~3~‐S)~2~PtL~2~}~x~ML′~y~]^z^ aggregates. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)