title: Formation of the heterocumulene anion SCCCN(-) by a cyano migration from the radical anion of 1,2-dicyanoethylenedithiolate.
abstract: The anionic heterocumulene SCCCN(-) was generated in the gas phase by collisional activation of the radical anion of 1,2-dicyanoethylenedithiolate. The mechanism of this reaction, as well as the structures of neutral and anionic products, was investigated by hybrid density functional theory (DFT) calculations. Dissociation to form SCCCN(-) and SCN is proposed to occur by a radical directed cyano migration reaction, with calculations suggesting this is the lowest energy fragmentation pathway available to the precursor anion. In contrast, the even-electron protonated 1,2-dicyanoethylenedithiolate anion fragmented by loss of HCN.
authors.affiliation: School of Chemistry, The University of Melbourne, Victoria, Australia.
authors.forename: Tom
authors.initials: T
authors.lastname: Waters
authors.forename: Stephen J
authors.initials: SJ
authors.lastname: Blanksby
authors.forename: Lianyi
authors.initials: L
authors.lastname: Zhang
authors.forename: Richard A J
authors.initials: RA
authors.lastname: O'Hair