Group 10 Metal Benzene-1,2-dithiolate Derivatives in the Synthesis of Coordination Polymers Containing Potassium Countercations

The use of theoretical calculations has allowed us to predict the coordination behavior of dithiolene [M­(SC<sub>6</sub>H<sub>4</sub>S)<sub>2</sub>]<sup>2–</sup> (M = Ni, Pd, Pt) entities, giving rise to the first organometallic polymers {[K<sub>2</sub>(μ-H<sub>2</sub>O)<sub>2</sub>]­[Ni­(SC<sub>6</sub>H<sub>4</sub>S)<sub>2</sub>]}<sub><i>n</i></sub> and {[K<sub>2</sub>(μ-H<sub>2</sub>O)<sub>2</sub>(thf)]<sub>2</sub>[K<sub>2</sub>(μ-H<sub>2</sub>O)<sub>2</sub>(thf)<sub>2</sub>]­[Pd<sub>3</sub>(SC<sub>6</sub>H<sub>4</sub>S)<sub>6</sub>]}<sub><i>n</i></sub> by one-pot reactions of the corresponding d<sup>10</sup> metal salts, 1,2-benzenedithiolene, and KOH. The polymers are based on σ,π interactions between potassium atoms and [M­(SC<sub>6</sub>H<sub>4</sub>S)<sub>2</sub>]<sup>2–</sup> (M = Ni, Pd) entities. In contrast, only σ interactions are observed when the analogous platinum derivative is used instead, yielding the coordination polymer {[K<sub>2</sub>(μ-thf)<sub>2</sub>]­[Pt­(SC<sub>6</sub>H<sub>4</sub>S)<sub>2</sub>]}<sub><i>n</i></sub>.