Splitting of the 2nd d-d band of trans-(CoCl2N4)X-type complexes observed in the solid state at 113K.

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概要

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• The electronic spectra of <I>trans</I>-[CoCl<SUB>2</SUB>(NH<SUB>3</SUB>)<SUB>4</SUB>]Cl and its analogues measured in the solid state at 113 K show four ligand field bands assignable to the Ia(<SUP>1</SUP>E<SUB>g</SUB><SUP>a</SUP>← <SUP>1</SUP>A<SUB>1g</SUB>), Ib(<SUP>1</SUP>A<SUB>2g</SUB>← <SUP>1</SUP>A<SUB>1g</SUB>), IIa(<SUP>1</SUP>B<SUB>2g</SUB>← <SUP>1</SUP>A<SUB>1g</SUB>), and IIb(<SUP>1</SUP>E<SUB>g</SUB><SUP>b</SUP>← <SUP>1</SUP>A<SUB>1g</SUB>) transitions in D<SUB>4h</SUB> approximation. The ligand field parameters obtained from the observed data are; <I>e</I><SUB>σ</SUB>(N)=7400–8000 cm<SUP>−1</SUP>, <I>e</I><SUB>σ</SUB>(Cl)=4500–5400 cm<SUP>−1</SUP>, <I>e</I><SUB>π</SUB>(Cl)=300–830 cm<SUP>−1</SUP>, and the Racah's parameter <I>C</I> estimated with the assumption of <I>C</I>=4<I>B</I> is ca. 2000 cm<SUP>−1</SUP>. A nearly linear relationship is obtained between the <I>e</I><SUB>σ</SUB>(Cl) and <I>e</I><SUB>π</SUB>(Cl) values; the stronger the coordination of Cl<SUP>−</SUP> to Co(III), the stronger the π interaction of Cl<SUP>−</SUP> with Co(III).

• 公益社団法人 日本化学会の論文

著者

• Tsuchimoto Masanobu

  Department Of Chemistry Chiba Institute Of Technology

• Fujita Junnosuke

  Department of Chemistry Faculty of Science Osaka University

• Kita Masakazu

  Department of Chemistry, Faculty of Science, Nagoya University

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