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Gas‐phase Reactions of Isomeric Carbene and Distonic Radical Anions Derived from Methylthioacetonitrile with Dimethyl Disulfide
Author(s) -
Kauw Jack,
Born Monique,
Ingemann Steen,
Nibbering Nico M. M.
Publication year - 1996
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/(sici)1097-0231(199608)10:11<1400::aid-rcm656>3.0.co;2-3
Subject(s) - chemistry , carbene , disulfide bond , dimethyl disulfide , phase (matter) , gas phase , photochemistry , organic chemistry , catalysis , sulfur , biochemistry
The gas‐phase ion/molecule reactions of the CH 3 SCDCN, CH 3 SCCN and · CH 2 SCDCN ions formed in the reaction of the O −· ion with CH 3 SCD 2 CN have been studied with the use of Fourier‐transform ion cyclotron resonance (FTICR). In the reaction of the CH 3 SCDCN carbanion with the model substrate, dimethyl disulfide, a CH 3 SD molecule is expelled from the collision complex with the indicated formation of a (CH 3 S) 2 CCN ion. In the reactions of the carbene radical anion, CH 3 SCCN, loss of a CH 3 S · radical occurs and the formation of an ion with a (CH 3 S) 2 CCN structure is again indicated. A distinct reactivity is observed for the distonic radical anion, · CH 2 SCDCN, which reacts with dimethyl disulfide by the competing losses of CH 3 SH and CH 3 S · from the collision complex. It is proposed that the loss of CH 3 SH yields a CH 3 SĊHSCDCN or CH 3 SCHSĊDCN radical anion, whereas the loss of CH 3 S · is proposed to lead to a CH 3 SCH 2 SCDCN carbanion. The formation of these species in the reactions of the · CH 2 SCDCN ion is discussed as involving an initial radical or nucleophilic attack on one of the sulfur atoms in dimethyl disulfide followed by cleavage of the sulfur–sulfur bond prior to the loss of a CH 3 SH molecule and/or a CH 3 S · radical.