Formation of the heterocumulene anion SCCCN(-) by a cyano migration from the radical anion of 1,2-dicyanoethylenedithiolate.
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.
Waters
Tom
T
School of Chemistry, The University of Melbourne, Victoria, Australia.
Blanksby
Stephen J
SJ
Zhang
Lianyi
L
O'Hair
Richard A J
RA