Wydział Chemii

G. S. Denisov

Aleksander Koll

V. I. Lobadyuk

V. M. Schreiber

A. Shurukhina

V. N. Spevak

2002

Journal of Molecular Structure

605

221-226

10.1016/S0022-2860(01)00783-9

Naukowa

Angielski

Artykuł

DFT calculations of vibrational spectra and structural parameters of dimethylsulfoxide (DMSO) molecule, its hydrogen bonded complex with HCl, mono- and bis-dimethylsulfoxide cations DMSOH⁺ and DMSOHOSDM⁺ have been performed at B3LYP/6-31G^∗∗ level. The results obtained for free DMSO and DMSO+HCl complex are in good agreement with the known experimental data. For free homoconjugated cation (DMSOHOSDM)⁺, an extremely short and a practically linear hydrogen bond with nearly central position of the bridging proton have been found. The addition of a counterion leads to lengthening and bending of the hydrogen bond. A solid [(DMSO)₂H]₂[PtCl₆] compound has been synthesized and the IR spectrum of this salt has been investigated. The structural parameters and vibrational frequencies calculated for [(DMSO)₂H]⁺X⁻ complexes were found to be in good agreement with experimental X-rays and IR data for solid [(DMSO)₂H]₂[PtCl₆]. The most important feature of vibrational spectrum of homoconjugated bis-dimethylsulfoxide cation is the essential involvement of proton stretching and bending coordinates in different normal modes, resulting in mixing of proton vibrations with vibrations of sulfoxide moiety, particularly with νSO, νCS, δCH.

Hydrogen bond, Homoconjugated cation, Vibrational spectrum, Dimethylsulfoxide

https://doi.org/10.1016/S0022-2860(01)00783-9

http://www.elsevier.com