Theoretical investigation of the relative stabilities of <i>X</i>SS<i>X</i> and <i>X</i><sub>2</sub>SS isomers (<i>X</i> = F, Cl, H, and CH<sub>3</sub>)

Journal of Computational Chemistry - Tập 16 Số 4 - Trang 465-477 - 1995
F. Matthias Bickelhaupt1, Miquel Solà1,2, Paul von Ragué Schleyer1
1Computer Chemie Centrum, Institut für Organische Chemie, Universität Erlangen-Nürnberg, Henkestr. 42, D-91054 Erlangen, Germany
2Institut de Química Computacional and Departament de Química, Universitat de Girona, Plaça de l'Hospital 6, 17071 Girona, Catalonia, Spain.

Tóm tắt

AbstractThe structures and relative stabilities of a series of disulfide (XSSX) and thiosulfoxide (X2SS) isomers have been studied for X = F, Cl, CH3, and H, using various levels of conventional ab initio and density functional theory (DFT). The XSSX isomers are more stable than the X2SS isomers for all substituents. The energy gap ΔE(X) between the two isomers increases (i.e., XSSX becomes more stable with respect to X2SS), and the SS bond contracts in the series for X = F, Cl, CH3, H. The results are interpreted by means of natural population analysis (NPA) (e.g., the interaction between the disulfide moiety S and the two substituents X·). The bonding in the hypervalent X2SS species is similar to the bonding in the nonhypervalent XSSX and does not involve a special role for sulfur‐3d orbitals. These orbitals acquire only minimal populations and are not to be conceived as valence orbitals. The DFT and conventional ab initio results, Xα/DZP and MP2/6‐31G** optimized structures and isomerization energies (at the highest levels of both methods), agree well. © 1995 by John Wiley & Sons, Inc.

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Journal of Computational Chemistry

Tập 16 Số 4

465-477

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