Circular dichroism spectra and their relation to asymmetric distortion of some dimeric molybdenum(V) complexes containing optically active amino carboxylate.

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概要

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• Circular dichroism (CD) spectra of fifteen kinds of μ-X-μ-Y-bis(oxomolybdenum(V)) complexes, where X=Y=O, X=O and Y=S, and X=Y=S, containing optically active ligands such as (<I>S</I>)-cysteinate, its alkyl esters, (<I>R</I>)-penicillaminate (<I>R</I>-pen), (<I>S</I>)-histidinate, and (<I>R</I>)-propylenediaminetetraacetate, give two distinctive peaks with opposite signs at <I>ca.</I> 26000 and 33000 cm<SUP>−1</SUP> in various media including KBr disks. Close examination of the known X-ray structural data of eight complexes indicated that the pseudo-octahedral coordination sphere of two molybdenum(V) ions are asymmetrically twisted around the Mo–Mo axis. The direction of such a twist for the complexes containing the ester ligands and <I>R</I>-pen, is opposite to that for the complexes with other ligands. The former and latter complexes give positive and negative, and negative and positive CD peaks at <I>ca.</I> 26000 and 33000 cm<SUP>−1</SUP>, respectively. Thus the CD signs of the two peaks are related to the asymmetric distortion around the Mo–Mo axis.

• 公益社団法人 日本化学会の論文

著者

• Sasaki Yoichi

  Department Of Chemistry Faculty Of Science Hokkaido University

• Saito Kazuo

  Department Chemistry Faculty Of Science Tohoku University

• Suzuki Kimiko

  Department of Chemistry, Faculty of Science, Tohoku University

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