Dynamic behavior of acetylacetonato, triphenylphosphine and alkyl ligands in NiR(acac)(PPh3)n (R=C2H5, CH3) in solution and disproportionation of the alkylnickel complexes in pyridine.
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Dynamic behavior of acetylacetonato (acac), triphenylphosphine (PPh<SUB>3</SUB>) and ethyl (in the case of <B>1</B>) ligands of NiR(acac)(PPh<SUB>3</SUB>)<I><SUB>n</SUB></I> (R=C<SUB>2</SUB>H<SUB>5</SUB>, <I>n</I>=1 (<B>1</B>); R=CH<SUB>3</SUB>, <I>n</I>=2 (<B>2</B>)) in solution has been studied. PPh<SUB>3</SUB> ligand(s) in <B>1</B> and <B>2</B> exchange rapidly on NMR time scale with free PPh<SUB>3</SUB> in solution. Addition of excess PPh<SUB>3</SUB> makes the exchange rate much faster and an <I>S</I><SUB>N</SUB>2 mechanism is proposed to explain the acceleration effect. <SUP>31</SUP>P-NMR spectrum of <B>1</B> in pyridine shows that the PPh<SUB>3</SUB> ligand is replaced by the solvent molecule. Acac ligands in <B>1</B> and <B>2</B> also undergo rapid interchange on NMR time scale. The activation energy for the acac interchange is about 10 kcal/ mol. On standing a specifically deuterated ethylnickel complex, Ni(CH<SUB>2</SUB>CD<SUB>3</SUB>)(acac)(PPh<SUB>3</SUB>) <B>1</B>-<I>d</I><SUB>3</SUB> in solution, the hydrogens and deuteriums in the ethyl group were scrambled. Appearance of the methyl proton signals in the <SUP>1</SUP>H-NMR spectrum of the deuterated ethylnickel complex after the treatment in solution demonstrates the occurrence of the H–D scrambling in solution. Both <B>1</B> and <B>2</B> undergo disproportionation reactions in pyridine. The rate of the disproportionation is second-order with respect to the concentration of <B>2</B>.
- 公益社団法人 日本化学会の論文
著者
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NAKAMURA Yoshiyuki
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
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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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Saruyama Toshio
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
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