A Conformational Study of the NO<I><SUB>x</SUB></I>(<I>x</I>=1 or 2)-catalyzed Isomerization of <I>cis</I>-2-Butene Using the INDO-UHF Method
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概要
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The NO<I><SUB>x</SUB></I>(<I>x</I>=1 or 2)-catalyzed isomerization of <I>cis</I>-2-butene was investigated by means of the INDO-UHF theory, with a particular view to the energetic and conformational aspects of the reaction. The NO<SUB>2</SUB>-addition process to form the intermediate radical (R<SUB>1</SUB>) had no appreciable activation barrier, although the NO<SUB>2</SUB>-fission process from the intermediate radical (R<SUB>2</SUB>) had the C-NO<SUB>2</SUB> dissociation energy of 44.6 kcal/mol. Some characteristic features of the stretched C-C bond in the intermediate radical (R<SUB>1</SUB>) were; (1) <I>r</I><SUB>cc</SUB>=1.45 Å, which was roughly equal to the value (1.481 Å) in <I>cis</I>-2-butene at the transition state of its thermal isomerization; (2) a pseudo π-conjugation with a small π-character (about 13% of <I>E</I><SUB>CC</SUB><SUP>R</SUP>) in comparison with that (about 29% of <I>E</I><SUB>CC</SUB><SUP>R</SUP>) in <I>cis</I>-2-butene, and (3) approximately the same magnitude of the hfsc value (34.40–34.47 G) for the sp<SUP>2</SUP>-hydrid carbon as that (experimental value of 39.07 G) for the said atom in the ethyl radical. The calculated internal-rotation barrier of the intermediate radical (R<SUB>1</SUB>) around the C–C bond (1.75–3.01 kcal/mol in the two rotating directions) was smaller than that (around 4 kcal/mol) obtained from the thermodynamic estimations. The energetically most stable or unstable rotamer was found in the staggered or the eclipsed configuration respectively; a hydrogen-bonding effect on the stabilization was observed in staggered configuration, although a remarkable effect of the homoconjugation or the repulsive interaction of unpaired and lone-paired electrons can be disregarded in the present internal-rotamer.
- 公益社団法人 日本化学会の論文
著者
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OHKUBO Katsutoshi
Department of Applied Chemistry and Biochemistry, Faculty of Engineering, Kumamoto University
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Okada Masahide
Department Of Electrical Engineering And Bioscience Waseda University
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Ikebe Hiromichi
Department of Synthetic Chemistry, Faculty of Engineering, Kumamoto University
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