Formation of the heterocumulene anion SCCCN? by a cyano migration from the radical anion of 1,2-dicyanoethylenedithiolateDedicated to Professor John H. Bowie on the occasion of his 65th Birthday and in recognition to his pioneering work on the gas phase chemistry of anions.
Waters, Tom; Blanksby, Stephen J.; Zhang, Lianyi; O'Hair, Richard A. J.; Waters Tom; School of Chemistry, The University of Melbourne; Blanksby Stephen J.; Department of Chemistry, The University of Wollongong; Zhang Lianyi; School of Chemistry, The University of Melbourne; O'Hair Richard A. J.; School of Chemistry, The University of Melbourne
Журнал:
Organic & Biomolecular Chemistry
Дата:
2004
Аннотация:
The anionic heterocumulene SCCCN<sup>â </sup> 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<sup>â </sup> 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.
195.6Кб