Radical anions of 1,1-azoliumdithiocarboxylates

Abstract

The 1,1-azoliumdithiocarboxylate cAACMe-CS2 (1a) was prepared and its redox chemistry was evaluated and compared to NHC-based dithiocarboxylates IDipp CS2 (1b) and IMes-CS2 (1c). Radical anions [carbene CS2]·– were prepared by metallic reduction as the potassium or magnesium ion complexes [K(18 crown 6)(cAACMe-CS2)] (2a), [K(18 crown 6)(NHC-CS2)] (NHC = IDipp: 2b, IMes: 2c), and [Mg(DippNacNac)(cAACMe-CS2)] (3) and extensively characterized (SC-XRD, EPR, UV/VIS/NIR, DFT). These complexes represent the first examples of isolated radical anions of 1,1 dithiolenes.