An analysis of the through-bond interaction using the localized molecular orbitals—II : Long-range proton hyperfine coupling in bridgehead alkyl radicals: bicyclo[1.1.1]pent-1-yl,bicyclo[2.1.1]hex-1-yl and bicyclo[2.2.1]hept-1-yl radicals |
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Authors: | Masaru Ohsaku Akira Imamura Kimihiko Hirao Takashi Kawamura |
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Institution: | Department of Chemistry, Faculty of Science, Hiroshima University, Higashisenda-machi, Hiroshima 730, Japan;Department of Chemistry, Shiga University of Medical Science, Setatsukinowa-cho, Otsu, Shiga 520-21, Japan;Department of Hydrocarbon Chemistry, Faculty of Engineering, Kyoto University, Kyoto 606, Japan |
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Abstract: | The INDO calculations were performed on three bridgehead alkyl radicals; bicyclo1.1.1]pent-1-yl, bicyclo2.1.1]hex-l-yl and bicyclo2.2.1]hept-1-yl radicals. We have transformed the canonical molecular orbitals obtained by the INDO method into the localized molecular orbitals. With the use of the obtained localized molecular orbitals, the variation in the hyperfine coupling constant at the bridgehead proton in these radicals was pursued in terms of the through-bond (and/or the through-space) interaction according to the method by which we selectively can pick up a particular interaction between the specified localized molecular orbitals in a radical. As a result of this analysis, it was found that the hyperfine coupling constants in these radicals can be expressed by the summation of several terms; through-virtuals, through-space, through-bond, and some other coupling terms. |
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