Photoelectron spectra and electronic structures of some chlorosulfonyl pseudohalides.
The electronic structures of chlorosulfonyl pseudohalide ClSO2X (X = Cl, NCO, N3) are studied by photoelectron spectroscopy (PES) combined with the OVGF calculation at 6-311++G(3df) basis sets. The first ionization potentials for ClSO2NCO and ClSO2N3 are determined to be 12.02 and 11.43 eV, respectively, for the first time, and their features in the PE spectra were assigned based on comparison with related compounds and with high level quantum calculations. Photoelectron spectra of ClSO2NCO and ClSO2N3 suggest that the interactions between chlorine "lone-pair" electrons and two pseudohalogen groups have significant effect on the HOMOs of two compounds, besides the influence of their electronegativity on the first ionization energies.
State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China.
Liu
L
Fengyi
Zeng
Z
Xiaoqing
Wang
W
Weigang
Meng
M
Lingpeng
Zheng
Z
Shijun
Ge
G
Maofa
Wang
W
Dianxun
D001386:Azides / Q000737:chemistry*; D002712:Chlorides / Q000737:chemistry*; D004583:Electrons; D017953:Isocyanates / Q000737:chemistry*; D015394:Molecular Structure; D010777:Photochemistry; D013441:Sulfinic Acids / Q000737:chemistry*
D001386:Azides; D002712:Chlorides; D017953:Isocyanates; D013441:Sulfinic Acids; C508919:chlorosulfonyl azide; C487390:chlorosulfonyl isocyanate; C044255:sulfonyl chloride