K. Ohkubo, T. Yamabe
May 1, 1971
Citations
0
Influential Citations
10
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
The interaction between sulfonium salts and molecular oxygen was studied by the ASMO SCF method. Firstly, the results of the ASMO SCF calculation of trimethylsulfonium chloride suggested that the bond between the sulfonium cation and the anion was constituted mainly of the bonding (d-p)π-type overlaps (made by 3dyz-(or 3dxz-) of S and 3py (or 3px) of Cl) and of the antibonding (d-p)σ-type overlaps (made by 3dz2 (or 3pz) of S and 3pz (or 3dz2) of Cl). Secondly, the sulfonium salt interacts with molecular oxygen mainly through a (d-p)σ-type overlap between the 3dyz-(or 3dxz-)orbital of the former and the (1πg)z-orbital of the latter. Thirdly, a maximum overlap formed between 3d-sulfur orbitals and 1πg-orbitals of O2 is established at the O2-rotation angle of π/4 to the direction of the d-orbital expansion. Finally, the change in the energy state of O2 caused by the sulfonium-salt interaction was discussed.