Study of organo(2,2'-bipyridine)nickel complexes. III. NMR studies on the interaction of dialkyl(2,2'-bipyridine)nickel with solvents and olefins.
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概要
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The <SUP>1</SUP>H-NMR spectra of NiR<SUB>2</SUB>(bpy)(bpy=2,2′-bipyridine; R=CH<SUB>3</SUB>, C<SUB>2</SUB>H<SUB>5</SUB>, and C<SUB>3</SUB>H<SUB>7</SUB>) and Ni(C<SUB>2</SUB>H<SUB>5</SUB>)<SUB>2</SUB>(bpy)–olefin systems (olefin=acrylonitrile and acrylaldehyde) have been studied in a temperature range from −70 °C to 80 °C. The temperature dependence of the chemical shifts of ethyl and 2,2′-bipyridine protons of Ni(C<SUB>2</SUB>H<SUB>5</SUB>)<SUB>2</SUB>-(bpy) in non-aromatic solvents (acetonitrile, <I>N</I>,<I>N</I>-dimethylformamide, acetone and tetrahydrofuran) is analyzed on the basis of the formation of 1: 1 solvent-solute complex. The formation constant of the 1: 1 comples, <I>K</I><SUB>1</SUB>, and the thermodynamic parameters <I>ΔF</I><SUB>1</SUB><SUP>°</SUP>, <I>ΔH</I><SUB>1</SUB><SUP>°</SUP>, and <I>ΔS</I><SUB>1</SUB><SUP>°</SUP> are given. The NMR spectra of NiR<SUB>2</SUB>(bpy) in aromatic solvents show the aromatic induced solvent shifts, and the chemical shifts of CH<SUB>2</SUB> and CH<SUB>3</SUB> of Ni(C<SUB>2</SUB>H<SUB>5</SUB>)<SUB>2</SUB>(bpy) coincide at 76 °C in benzene to give a sharp singlet peak. The <SUP>13</SUP>C-NMR spectrum of Ni(C<SUB>2</SUB>H<SUB>5</SUB>)<SUB>2</SUB>(bpy) in benzene shows a triplet at 10.63 ppm (CH<SUB>2</SUB>, <I>J</I>(<SUP>13</SUP>C–H)=132 Hz) and a quartet at 15.97 ppm (CH<SUB>3</SUB>, <I>J</I>(<SUP>13</SUP>C–H)=128 Hz). The formation constant of Ni(C<SUB>2</SUB>H<SUB>5</SUB>)<SUB>2</SUB>(bpy)(olefin), <I>K</I><SUB>2</SUB>, and the thermodynamic parameters, <I>ΔF</I><SUB>2</SUB><SUP>°</SUP>, <I>ΔH</I><SUB>2</SUB><SUP>°</SUP>, and <I>ΔS</I><SUB>2</SUB><SUP>°</SUP> have been obtained from the temperature dependence of the NMR spectra of the Ni(C<SUB>2</SUB>H<SUB>5</SUB>)(bpy)–olefin systems. The values of the chemical shift differences between CH<SUB>2</SUB> and CH<SUB>3</SUB> (<I>Δ</I>=δ<SUB>CH<SUB>2</SUB></SUB>–δ<SUB>CH<SUB>3</SUB></SUB>) for Ni(C<SUB>2</SUB>H<SUB>5</SUB>)<SUB>2</SUB>(bpy), Ni(C<SUB>2</SUB>H<SUB>5</SUB>)<SUB>2</SUB>-(bpy) (acrylaldehyde), and Ni(C<SUB>2</SUB>H<SUB>5</SUB>)<SUB>2</SUB>(bpy)(acrylonitrile) are −0.30, 0.94 and 0.83, respectively. The increase of the values of <I>Δ</I> by the coordination of the electronegative olefins with nickel is regarded as indicating the increase of the electronegativity of nickel due to the back-donation from nickel to the olefin.
- 公益社団法人 日本化学会の論文
著者
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Yamamoto Takakazu
Research Laboratory Of Resouces Utilization Tokyo Institute Of Technology
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Nakamura Yoshiyuki
Research Laboratory Of Resources Utilization Tokyo Institute Of Technology
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Yamamoto Akio
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
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