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(SC6H4S)(2)](2-) (M = Ni, Pd, Pt) entities, giving rise to the first organometallic polymers {[K-2(mu-H2O)(2)][Ni(SC6H4S)(2)]}n and {[K-2(mu-H2O)(2)(thf)](2)[K-2(mu-H2O)(2)(thf)(2)][Pd-3(SC6H4S)(6)]}(n) by one-pot reactions of the corresponding d10 metal salts, 1,2-benzenedithiolene, and KOH. The polymers are based on sigma,pi interactions between potassium atoms and [M(SC6H4S)(2)](2-) (M = Ni, Pd) entities. In contrast, only s interactions are observed when the analogous platinum derivative is used instead, yielding the coordination polymer {[K-2(mu-thf)(2)][Pt(SC6H4S)(2)]}(n).