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Gas‐Phase Spectroscopy of the Unstable Sulfur Diisocyanate Molecule S(NCO) 2
Author(s) -
Wang Weigang,
Ge Maofa,
Yao Li,
Zeng Xiaoqing,
Sun Zheng,
Wang Dianxun
Publication year - 2006
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200600084
Subject(s) - chemistry , dissociation (chemistry) , mass spectrometry , molecule , ionization , mass spectrum , cyanate , sulfur , spectroscopy , photochemistry , ionization energy , chemical ionization , x ray photoelectron spectroscopy , bond dissociation energy , computational chemistry , ion , organic chemistry , nuclear magnetic resonance , physics , chromatography , quantum mechanics
Sulfur diisocyanate is generated from a heterogeneous reaction of gaseous sulfur dichloride with silver cyanate and studied for the first time in the gas phase. Combined with quantum chemical calculations, the electronic structure is characterized by photoelectron spectroscopy (PES). Simultaneously, an investigation of the possible ionization and dissociation processes for the molecular cation is presented based on experimental soft ionization mass spectrometry. From the calculated bond‐dissociation energies, the dissociation pathway is determined. S(NCO) 2 + undergoes 1,3‐sigmatropic rearrangement with a smaller barrier height (9.9 kcal mol −1 ) than the neutral counterpart. Thus, the 1,3‐sigmatropic rearrangement is preferred for the molecular cation, and OCNCO + and NS + is produced by subsequent dissociation of the rearrangement product. The analysis agrees very well with the experimental mass spectrum.