ABSTRACT
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.
Subject(s)
Azides/chemistry , Chlorides/chemistry , Isocyanates/chemistry , Sulfinic Acids/chemistry , Electrons , Molecular Structure , PhotochemistryABSTRACT
Pure INCO, ISCN, and the hitherto unknown molecule ISeCN have been prepared in the HeI photoelectron spectrometer (PES) by the heterogeneous reactions of ICl gas with AgNCO, AgSCN at room temperature, and AgSeCN at -9 (+/- 1) degrees C, respectively. They were characterized on line by PES experiments and OVGF calculations. The well-matched results between the PES experiments and OVGF calculations not only show that the new reaction is a good reaction to prepare pure INCO and pure ISCN, but also that the new compound prepared by passing the ICl gas over the freshly AgSeCN powder at -9 (+/- 1) degrees C is the hitherto unknown ISeCN.
