Proton affinity of S-containing aromatic compounds: Implications for crude oil hydrodesulfurization

The electronic structure and proton affinities of a series of organosulfur compounds such as thiophene, dibenzothiophene and a series of their derivatives have been studied by means density functional theory. The molecular structure of these compounds and their protonated species has been obtained b...

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Bibliographic Details
Published in:Journal of molecular catalysis. A, Chemical Chemical, 2008-02, Vol.281 (1), p.79-84
Main Authors: García-Cruz, Isidoro, Valencia, Diego, Klimova, Tatiana, Oviedo-Roa, Raúl, Martínez-Magadán, José Manuel, Gómez-Balderas, Rodolfo, Illas, Francesc
Format: Article
Language:English
Subjects:
Catalysis
Chemistry
Exact sciences and technology
General and physical chemistry
HOMO
Hydrodesulfurization
LUMO
NICS
Proton affinity
Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
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Summary:The electronic structure and proton affinities of a series of organosulfur compounds such as thiophene, dibenzothiophene and a series of their derivatives have been studied by means density functional theory. The molecular structure of these compounds and their protonated species has been obtained by means of geometry optimization and characterized as potential energy surface minima by harmonic frequency analysis. The analysis of frontier orbitals, aromaticity and proton affinity permits one to make quantitative predictions about the difficulty to remove sulfur from these molecules. In particular, it is suggested that the proton affinities provide a descriptor of the activity of these molecules towards hydrodesulfurization. Highest occupied molecular orbital (HOMO), (a) thiophene, (b) benzothiophene, (c) dibenzothiophene and (d) 4,6-dimethyldibenzothiophene at B3LYP/6-311++G** level of theory. ▪
ISSN:1381-1169
1873-314X
DOI:10.1016/j.molcata.2007.08.031