Electronic Spectra and Structure of Bis(ethylene-1,2-dithiolato)nickel and Bis(propene-3-thione-1-thiolato)nickel

Abstract

The electronic ground states and spectra of Ni(S2C2H2)2 [bis(ethylene-1,2-dithiolato)Ni] and Ni(S2C3H3)2 [bis(propene-3-thione-1-thiolato)Ni] have been calculated with an INDO-type LCAO-MO CI program recently developed for treating systems containing transition-metal atoms. The ground-state descriptions obtained for these two compounds are consistent with the greater stability of Ni(S2C2H2)2 relative to Ni(S2C3H3)2 and also with the existence of mono- and dianions of the former. The electronic spectra of these compounds were assigned with utilization of extensive configuration interaction to describe the ground and excited states. The calculated transitions agree reasonably well with the energies and nature of the experimentally observed ones. In particular, low-energy transitions are found for Ni(S2C2H2)2, consistent with the observed spectra of Ni(S2C2R2)2-type compounds. These transitions are not found for Ni(S2C3R3)2, which is also in agreement with experiment. © 1982, American Chemical Society. All rights reserved.