STUDIES OF INTERMOLECULAR INTERACTIONS IN PLANAR METAL COMPLEXES III1 BIS(ETHYLENE-1,2-DITHIOLENE) COMPLEXES OF NICKEL, PALLADIUM, AND PLATINUM

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Abstract
The synthesis and characterization of nineteen new bis-dithiolene metal complexes of the type A n +[MS4C4H4 n-], where A+ = various organic cations, M = Ni, Pd, Pt, and n = 0, 1, are described. The results of redox, infrared, electronic spectral, and NMR measurements on these complexes support a monomeric, planar structure for the complex units both in solution and, with the exception of the neutral MS4C4H4 (M = Pd, Pt) derivatives, in the solid state. However, evidence for intermolecular interactions in these solids has been found on the basis of four-probe conductivity measurements. The conductivities of these complexes range from less than 10−10 ohm−1 cm−1 to ∼ 10−5 ohm−1 cm−1 and depend markedly on the nature of A+, M and n. On the basis of these measurements, empirical generalizations relating conductivity and the structural parameters A+ and M are derived. In addition, information regarding the dependence of the conductivity on the spacial relationship of the complex units in the solid is obtained from measurements on single crystals of NiS4C4H4 and PtS4C4H4 as a function of crystal-lographic direction. The implications of these results with regard to the electron transport mechanism in such solids are discussed.