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(SC6 H4 S)2 ]2- (M = Ni, Pd, Pt) entities, giving rise to the first organometallic polymers {[K2 (μ-H2 O)2 ][Ni(SC6 H4 S)2 ]}n and {[K2 (μ-H2 O)2 (thf)]2 [K2 (μ-H2 O)2 (thf)2 ][Pd3 (SC6 H4 S)6 ]}n by one-pot reactions of the corresponding d10 metal salts, 1,2-benzenedithiolene, and KOH. The polymers are based on σ,π interactions between potassium atoms and [M(SC6 H4 S)2 ]2- (M = Ni, Pd) entities. In contrast, only σ interactions are observed when the analogous platinum derivative is used instead, yielding the coordination polymer {[K2 (μ-thf)2 ][Pt(SC6 H4 S)2 ]}n .