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

Abstract

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

Copper dithiolene [Cu(SC6H2Cl2S)2]− units connected to alkaline/copper complexes: from ionic assemblies to discrete molecular entities and coordination polymers

“…Some of these compounds indicate that the sulfur donor atoms of the [Cu(SC 6 H 2 Cl 2 S) 2 ]entity and even the chloro substituents are able to anchor additional metal centres, specially softer ones, promoting a further polymerization. The electrical studies carried out in this work with 3 and 4 CPs as compare with those previously reported for related CPs based on metal-dithiolene entities bridged by alkali complexes, 20,[35][36][37] suggest that the electrical conductivity is limited to relatively low values, 10 -6 -10 -9 σ•cm -1 , probably because of the limitation in electric current passes through the group 1 metal complexes. These results indicate that the formation of electrically conductive of CPs based on metaldithiolene entities require more efficient connectors.…”

“…These values are in the range to those found for related CPs formed by metal-dithiolene entities bridged by alkali complexes. 20,[35][36][37]…”

Proton and Electron Transfer in the Formation of a Copper Dithiolene-Based Coordination Polymer

“…The incorporation of metal dithiolene complexes as building blocks in conjugated coordination polymers could, however, lead to materials with interesting cooperative properties. Dithiolene based coordination polymers reported in the literature mostly consist of nitrogen containing dithiolene complexes, which are further coordinating to alkali metal ions. − In these cases, however, the interaction between nitrogen and alkali metal atoms is of a rather ionic nature, which limits through-bond charge delocalization. One example, which provided great incentive for research on transition metal ion based coordination polymers, was published by Takaishi et al They synthesized the first electrically conductive (6 × 10 –4 S/cm at 300 K) and porous coordination polymer Cu­[Cu­(pdt) 2 ] (pdt 2– : 2,3-pyrazinedithiolate).…”

A Mixed-Valence Tetra-Nuclear Nickel Dithiolene Complex: Synthesis, Crystal Structure, and the Lability of Its Nickel Sulfur Bonds

“…Metal dithiolene complexes are generally able to form different types of networks by covalent [45] and non-covalent bonds [46], while extended networks with nickel centers are comparatively rare. In cases where two or more nickel ions are bridged by dithiolene sulfur donor atoms, the metal centers might adopt different or partial formal oxidation states.…”

“…H NMR (CDCl 3 , 300 MHz): δ, ppm = 7.94-8.05 (m, ortho-phenyl, 2H), 7.55-7.67 (m, para-phenyl, 1H), 7.43-7.54 (m, meta-phenyl, 2H), 5.73 (s, -CHBr, 1H), 4.27 (q, J = 6.9 Hz, -CH 2 , 2H), 1.23 ppm (t, J = 7.2 Hz, -CH 3 , 3H) 13. C NMR (CDCl 3 , 75 MHz): δ, ppm = 187.9 (PhC=O), 164.8 (C=O), 134.0 (C-phenyl), 133.0 (C-phenyl), 128.8 (C-phenyl), 128.6 (C-phenyl), 62.9 (CH 2 ),46.2 (CHBr), 13.5 (CH 3 ). APCI-MS (EI+): m/e calculated for C 11 H 11 BrO 3 : 269.99, Found: 270.99 ([M + H] + ).…”