A study of the ligand exchange reaction of tetrakis(.MU.-trifluoroacetato)dimolybdenum(II) in acetonitrile by 19F NMR spectroscopy.

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概要

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• The dimeric molybdenum(II) complex, Mo<SUB>2</SUB>(CF<SUB>3</SUB>COO)<SUB>4</SUB>, forms Mo<SUB>2</SUB>(CF<SUB>3</SUB>COO)<SUB>4</SUB>·(CH<SUB>3</SUB>CN)<SUB>2</SUB> in acetonitrile, where solvent molecules are attached to positions trans to the metal–metal bond (apical positions). The rate of ligand exchange between Mo<SUB>2</SUB>(CF<SUB>3</SUB>COO)<SUB>4</SUB> ((1.31–8.28)×10<SUP>−2</SUP> M; M=mol dm<SUP>−3</SUP>) and CF<SUB>3</SUB>COONa ((1.31–4.56)×10<SUP>−1</SUP> M) was measured in acetonitrile by the use of <SUP>19</SUP>F NMR spectroscopy. The rate is independent of the total concentration of CF<SUB>3</SUB>COONa and is linearly dependent on that of Mo<SUB>2</SUB>(CF<SUB>3</SUB>COO)<SUB>4</SUB>. The first-order rate constant (<I>k</I><SUB>ex</SUB>) is (1.1±0.2)×10<SUP>4</SUP> s<SUP>−1</SUP> (25 °C), and the activation parameters are Δ<I>H</I><SUP>\neweq</SUP>=(8.2±0.8) kcal mol<SUP>−1</SUP> and Δ<I>S</I><SUP>\neweq</SUP>=(−15±3) K<SUP>−1</SUP> mol<SUP>−1</SUP>. Under the given conditions the complex seems to exist as Mo<SUB>2</SUB>(CF<SUB>3</SUB>COO)<SUB>4</SUB>·CF<SUB>3</SUB>COO<SUP>−</SUP>, where the underlined ligand occupies one of the apical positions, and the following mechanism is proposed (solvent molecules are omitted; asterisks indicate the molecule substituting for the coordinated ligand).<BR>Mo<SUB>2</SUB>(CF<SUB>3</SUB>COO)<SUB>4</SUB>·CF<U><SUB>3</SUB></U>COO<SUP>−</SUP>+<SUP>*</SUP>CF<SUB>3</SUB>COO<SUP>−</SUP>\oversetfast\rightleftarrowsMo<SUB>2</SUB>(CF<SUB>3</SUB>COO)<SUB>4</SUB>·<U><SUP>*</SUP></U>CF<U><SUB>3</SUB></U>COO<SUP>−</SUP>+CF<SUB>3</SUB>COO<SUP>−</SUP><BR>Mo<SUB>2</SUB>(CF<SUB>3</SUB>COO)<SUB>4</SUB>·<U><SUP>*</SUP></U>CF<U><SUB>3</SUB></U>COO<SUP>−</SUP>\overset<I>k</I><SUB>s</SUB>→Mo<SUB>2</SUB>(CF<SUB>3</SUB>COO)<SUB>3</SUB>(<SUP>*</SUP>CF<SUB>3</SUB>COO)·CF<U><SUB>3</SUB></U>COO<SUP>−</SUP><BR>The <I>k</I><SUB>ex</SUB> corresponds to <I>k</I><SUB>s</SUB>.

• 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

• Iwaizumi Masamoto

  Chemical Research Institute of Non-Aqueous Solutions, Tohoku University

• Migita Kouto

  Chemical Research Institute of Non-aqueous Solutions, Tohoku University

• Teramoto Kazunori

  Department of Chemistry, Faculty of Science, Tohoku University

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