Preparation and properties of nickel-phosphine complexes coordinated with .ALPHA.,.BETA.-unsaturated ester.
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概要
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Reactions of bis(1,5-cyclooctadiene)nickel, Ni(cod)<SUB>2</SUB>, with α,β-unsaturated esters in the presence of tertiary phosphine give a series of nickel-phosphine complexes formulated as Ni(tertiary phosphine)<I><SUB>n</SUB></I>L(L=alkyl methacrylates, methyl acrylate, or methyl cinnamate; <I>n</I>=2 for P(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>3</SUB>, P(C<SUB>2</SUB>H<SUB>5</SUB>)(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>2</SUB>, P(CH<SUB>3</SUB>)<SUB>2</SUB>(C<SUB>6</SUB>H<SUB>5</SUB>), P(C<SUB>2</SUB>H<SUB>5</SUB>)<SUB>3</SUB>, <I>n</I>=1 for P(cyclo-C<SUB>6</SUB>H<SUB>11</SUB>)<SUB>3</SUB>). Elemental analyses, IR and NMR spectra, and chemical properties of the complexes confirm the molecular formula. The olefinic proton signals of methyl acrylate and alkyl methacrylates coordinated to nickel shift to upfield by 2.6–4.9 ppm from those of free olefins in the <SUP>1</SUP>H-NMR spectra, indicating that the α,β-unsaturated esters coordinate to nickel through the double bond. The IR spectra show only small low frequency shifts of the ν(C=O) bands of the α,β-unsaturated esters on complex formation. The reactions of Ni(P-(C<SUB>6</SUB>H<SUB>5</SUB>)<SUB>3</SUB>)<SUB>2</SUB> (ethyl methacrylate) and Ni(P(cyclo-C<SUB>6</SUB>H<SUB>11</SUB>)<SUB>3</SUB>) (ethyl methacrylate) with vinyl acetate at room temperature cause the scission of the C–O bond in vinyl acetate to yield ethylene and nickel acetate.
- 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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Ishizu Junichi
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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