Abstract
The gas-phase clustering reactions of OCS+, S +2 , H+(OCS), and C2H +5 ions with carbonyl sulfide (OCS) molecules were studied using a pulsed electron-beam high-pressure mass spectrometer and applying density functional theory (DFT) calculations. In the cluster ions OCS+(OCS) n and H+(OCS)(OCS) n , a moderately strong, here referred to as “semi-covalent”, bond was formed with n=1. However, the nature of bonding changed from semi-covalent to electrostatic with n=1 → 2. The bond energy of S +2 (OCS) was determined experimentally to be 12.9±1 kcal/mol, which is significantly smaller than that of the isovalent S +2 (CS2) complex (30.9±1.5 kcal/mol). DFT based calculations predicted the presence of several isomeric structures for H+(OCS)(OCS) n complexes. The bond energies in the C2H +5 (OCS) n clusters showed an irregular decrease for n=1 → 2 and 7 → 8. The nonclassical bridge structure for the free C2H +5 isomerized to form a semi-covalent bond with one OCS ligand, [H3CCH2...SCO]+, i.e., reverted to classical structure. However, the nonclassical bridge structure of C2H +5 was preserved in the cluster ions C2H +5 (OCS) n below 140 K attributable to the lack of thermal energy for the isomerization. DFT calculations revealed that stability orders of the geometric isomers of H+(OCS)(OCS) n and C2H +5 (OCS) n changed with increasing n values.
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Published online September 26, 2005
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Hiraoka, K., Fujita, K., Ishida, M. et al. Thermochemical stabilities and structures of the cluster ions OCS+, S +2 , H+(OCS), and C2H +5 with OCS molecules in the gas phase. J Am Soc Mass Spectrom 16, 1760–1771 (2005). https://doi.org/10.1016/j.jasms.2005.07.007
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DOI: https://doi.org/10.1016/j.jasms.2005.07.007