Preparation, and structural and spectroscopic characterization of cobalt(III) phosphine complexes of the type, (Co(CN)4-2n(acac)n(P)2)(n-1)+ (acac=acetylacetonate ion, n=0,1,2, and P=P(CH3)x(C6H5)3-x, x=0,1,2,3).

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概要

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• A series of the complexes, [Co(CN)<SUB>4−2<I>n</I></SUB>(acac)<I><SUB>n</SUB></I>(P)<SUB>2</SUB>]<SUP>(<I>n</I>−1)+</SUP> (acac=acetylacetonate ion, P=P(CH<SUB>3</SUB>)<I><SUB>x</SUB></I>(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>3−<I>x</I>)</SUB> and several related complexes were prepared. For [Co(acac)<SUB>2</SUB>(P)<SUB>2</SUB>]<SUP>+</SUP>, the P(CH<SUB>3</SUB>)<SUB>3</SUB> and P(CH<SUB>3</SUB>)(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>2</SUB> complexes afford only the <I>cis</I> and the <I>trans</I> isomers, respectively, while the P(CH<SUB>3</SUB>)<SUB>2</SUB>(C<SUB>6</SUB>H<SUB>5</SUB>) complex forms both <I>cis</I> and <I>trans</I> isomers. No P(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>3</SUB> ligand gave the bis(acac)-type complex. The <I>trans</I> isomers show a strong absorption band in the region of the first absorption band, which is assumed to involve charge transfer transitions between the cobalt(III) ion and a phosphine, while the <I>cis</I> isomers give usual absorption spectra, exhibiting the first d-d absorption band of medium intensity. The methyl and phenyl groups on a phosphorus atom in both <I>cis</I> and <I>trans</I> isomers show triplet signals in the <SUP>1</SUP>H and <SUP>13</SUP>C NMR spectra due to virtual coupling. A <I>trans</I>(P,P) configuration was assigned to all the complexes of [Co(CN)<SUB>2</SUB>(acac)(P)<SUB>2</SUB>] on the basis of the NMR and electronic spectra. For [Co(CN)<SUB>4</SUB>(P)<SUB>2</SUB>]<SUP>−</SUP>, a <I>trans</I> configuration was assigned from the electronic spectra.

• 公益社団法人 日本化学会の論文

著者

• Kashiwabara Kazuo

  Department Of Chemistry Faculty Of Science Nagoya University

• Shibata Muraji

  Department of Chemistry Faculty of Science Kanazawa University

• Fujita Junnosuke

  Department of Chemistry Faculty of Science Osaka University

• Ohishi Tomoji

  Department of Chemistry, Faculty of Science, Nagoya University

• Katoh Katsuaki

  Department of Applied Chemistry, Faculty of Engineering, Hiroshima University

• Katoh Katsuaki

  Department of Chemistry, Faculty of Science, Nagoya University

関連論文

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• タイトル無し
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