Reversible CO insertion into an Ni-C bond of alkyl(acetylacetonato)-(triphenylphosphine)nickel(II).
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概要
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Reaction of alkyl(acetylacetonato)(triphenylphosphine)nickel(II), RNi(acac)(PPh<SUB>3</SUB>)<I>n</I> (R=C<SUB>2</SUB>H<SUB>5</SUB>, <I>n</I>=1 (<B>1a</B>); R=CH<SUB>3</SUB>, <I>n</I>=2 (<B>1b</B>)) with carbon monoxide gives acyl(acetylacetonato)(triphenylphosphine)nickel(II) RCONi(acac) (PPh<SUB>3</SUB>) (R=C<SUB>2</SUB>H<SUB>5</SUB> (<B>2a</B>); R=CH<SUB>3</SUB> (<B>2b</B>)). Elemental analysis, IR and NMR spectra, and chemical properties of the acylnickel complexes support the structure. A variable temperature NMR spectroscopic study has revealed that the acac ligand in the acyl complexes exchanges rapidly in solution on NMR time scale. The acylnickel complexes <B>2a</B> and <B>2b</B> tend to decarbonylate at room temperature, the decarbonylation tendency of <B>2b</B> being greater than <B>2a</B>. They undergo further disproportionation according to the stoichiometry: 3RCONi(acac)(PPh<SUB>3</SUB>)→RCOR+Ni(CO)<SUB>2</SUB>(PPh<SUB>3</SUB>)<SUB>2</SUB>+Ni(acac)<SUB>2</SUB>+RNi(acac)(PPh<SUB>3</SUB>). The mechanism involving the cross coupling of the acylnickel complex with the alkylnickel complex is proposed for the reaction on the basis of formation of CH<SUB>3</SUB>COC<SUB>2</SUB>H<SUB>5</SUB> on reaction of <B>2a</B> with <B>1b</B>.
- 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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Yamamoto Akio
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
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Saruyama Toshio
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
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