[M(R-dmet)<sub>2</sub>] Bis(1,2-dithiolenes): a Promising New Class Intermediate between [M(dmit)<sub>2</sub>] and [M(R,R‘-timdt)<sub>2</sub>] (M = Ni, Pd, Pt)
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We report the first examples of metal dithiolenes belonging to the class [M(R-dmet)2] [R-dmet = formally monoreduced N-substituted thiazolidine-2,4,5-trithione; R = Et, M = Ni (1), Pd (2), Pt (3)]. A comparative spectroscopic, electrochemical, and density functional theory theoretical investigation indicates that [M(R-dmet)2] complexes show features intermediate between those of the dithiolenes belonging to the previously reported classes [M(R,R‘-timdt)2] and [M(dmit)2] (R,R‘-timdt = formally monoreduced N,N‘-disubstituted imidazolidine-2,4,5-trithione; dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato). UV−vis−near-IR spectroscopy and cyclic voltammetry/differential pulsed voltammetry measurements performed on 1 and 3 proved that the new dithiolenes are stable as neutral, monoanionic, and bianionic species and feature a near-IR electrochromic absorption falling at about 1000 and 1250 nm for neutral and monoanionic species, respectively.
