ZHANG Shi-guo*,a,b BIAN Heb LI Da-zhia YU Hong-chaob XIA Dao-hongb
(a Binzhou Key laboratory of material chemistry, Department of chemistry and Chemical Engineering, Binzhou university , Binzhou 256603) (b College of Chemistry and Chemical Engineering, China University of Petroleum(East China), Dongying 267061)
Abstract: The demethanation reactions of dimethyl sulfide by Fe+ on both quartet and sextet potential energy surfaces have been investigated using density functional theory (B3LYP) in conjunction with the DGDZVP and 6-311+G(d, p) basis sets. Geometries of the stationary points were completely optimized. The transition states were validated by the vibrational analysis and the internal reaction coordinate (IRC) calculations. The vibration analysis and the IRC analysis testified the authenticity of intermediates and transition states.The calculation results indicate that, along the energetically preferable sextet pathway, the demethanation reaction can occur through four elementary steps, that is, encounter complexation, C-S activation, b-H shift, and nonreactive dissociation. Whereas along the quartet PES, both the C-S and methyl C-H activation could result in the demethanation reaction, of which, the reaction involving C-S activation is calculated to be the main pathway with relative lower energy barriers and intermediates.
Key words: dimethyl sulfide; demethanation; reaction mechanism; density functional theory
E-mail: lining5891539@163.com
Journal of Molecular Catalysis, Vol. 24, Issue 5, 2010, 443~449
