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[M(R-dmet)2] Bis(1,2-dithiolenes):  a Promising New Class Intermediate between [M(dmit)2] and [M(R,R‘-timdt)2] (M = Ni, Pd, Pt)

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posted on 2005-12-26, 00:00 authored by M. Carla Aragoni, Massimiliano Arca, Francesco A. Devillanova, Francesco Isaia, Vito Lippolis, Annalisa Mancini, Luca Pala, Alexandra M. Z. Slawin, J. Derek Woollins
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.

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