Quantitative Estimates of π-Contact-term Contributions to the Lanthanideinduced Paramagnetic <SUP>1</SUP>H Shifts in Aniline and <I>m</I>-Toluidine
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概要
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The paramagnetic proton chemical shifts induced by a series of Ln(FOD)<SUB>3</SUB>(Ln=Pr, Eu, Dy, Ho, Er, and Yb) were observed for aniline and <I>m</I>-toluidine in CCl<SUB>4</SUB>. In an attempt to separate the pseudo-contact(pcs) and contact shift(cs) contributions, the spin-density distributions of the π-cation radicals or the Ni(AcAc)<SUB>2</SUB>-induced shifts were used for the cs pattern in a molecule, as well as the geometric factors for the pcs pattern. The appropriate regions of the two geometric parameters were determined by the computer-search method for the least-squares fits of the observed to the calculated shifts. Thus, the intramolecular average value of the ratio of cs-to-pcs contributions was evaluated. The variation in this ratio with an Ln ion corresponds relatively well to that of the theoretical ratio, |〈<I>S</I><SUB>Z</SUB>〉⁄|δ|, where 〈<I>S</I><SUB>z</SUB>〉 has been calculated by Golding <I>et al.</I> and where δ is the relative pcs predicted by Bleaney <I>et al.</I>
- 公益社団法人 日本化学会の論文
著者
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Hirayama Masatoshi
Department Of Chemistry Faculty Of Science Ibaraki University
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Saito Makoto
Department Of Bacteriology Aichi Prefectural Institute Of Public Health
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Takeuchi Makoto
Department Of Biology Faculty Of Science Okayama University
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Sato Michihiko
Department of Chemistry, Faculty of Science, Ibaraki University
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Saito Makoto
Department of Chemistry, Faculty of Science, Ibaraki University
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