A Theoretical Study of the Possible Interaction between Sulfonium Salts and Molecular Oxygen
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概要
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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 (<I>d</I>-<I>p</I>)π-type overlaps (made by 3<I>d<SUB>yz</SUB></I>-(or 3<I>d<SUB>xz</SUB></I>-) of S and 3<I>p<SUB>y</SUB></I> (or 3<I>p<SUB>x</SUB></I>) of Cl) and of the antibonding (<I>d</I>-<I>p</I>)σ-type overlaps (made by 3<I>d<SUB>z</SUB></I><SUP>2</SUP> (or 3<I>p<SUB>z</SUB></I>) of S and 3<I>p<SUB>z</SUB></I> (or 3<I>d<SUB>z</SUB></I><SUP>2</SUP>) of Cl). Secondly, the sulfonium salt interacts with molecular oxygen mainly through a (<I>d</I>-<I>p</I>)σ-type overlap between the 3<I>d<SUB>yz</SUB></I>-(or 3<I>d<SUB>xz</SUB></I>-)orbital of the former and the (1π<I><SUB>g</SUB></I>)<I><SUB>z</SUB></I>-orbital of the latter. Thirdly, a maximum overlap formed between 3<I>d</I>-sulfur orbitals and 1π<I><SUB>g</SUB></I>-orbitals of O<SUB>2</SUB> is established at the O<SUB>2</SUB>-rotation angle of π/4 to the direction of the <I>d</I>-orbital expansion. Finally, the change in the energy state of O<SUB>2</SUB> caused by the sulfonium-salt interaction was discussed.
- 公益社団法人 日本化学会の論文
著者
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Ohkubo Katsutoshi
Faculty of Engineering, Kumamoto University
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Yamabe Tokio
Faculty of Engineering, Kyoto University
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