The discovery of trigonal prismatic (TP) coordination in tris(dithiolene) complexes was stimulated by the efforts of Gray, Schrauzer, Holm and Davison in the 1960's on the chemistry of dithiolene complexes that showed multiple reversible electron transfer processes and challenged conventional oxidation state assignments.  The structures of Re(S2C2Ph2)3, V(S2C2Ph2)3 and Mo(S2C2H2)3 were reported and bonding pictures based on semiempirical molecular orbital calculations were presented. The basis for stability of TP coordination was put forward based on partial oxidation of the unsaturated 1,2-dithiolate ligands. The notion of redox-non-innocence in the tris dithiolene complexes has been revisited in recent work by Wieghardt and Sproules involving new experimental work and a reanalysis of the bonding in the molecular and electronic structures of Re(L)3n and V(L)3n complexes. A comparison is given between the early studies of the 1960's and the more recent, experimentally and computationally more complete studies.

Trigonal prismatic coordination in tris(dithiolene) complexes:  Realization of non-innocence

246th National Meeting (2013)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.