Preparation and properties of monoalkylnickel(II) complexes NiR(NR1R2)L2 having imido,imidazolato,or methyl phenylcarbamato-N ligand.
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概要
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Reactions of dialkylnickel(II) complexes NiR<SUB>2</SUB>L<SUB>2</SUB> 1 (R=CH<SUB>3</SUB>, C<SUB>2</SUB>H<SUB>5</SUB>; L=1/2 bpy(2,2′-bipyridine), 1/2 dpe (1,2-bis(diphenylphosphino)ethane), PEt<SUB>3</SUB>) with compounds having acidic N–H bonds (succinimide, phthalimide, diacetamide, pyromellitimide (1,2 : 4,5-benzenebis(dicarboximide)), imidazole) gave corresponding monoalkylnickel(II) complexes having Ni–N bond formulated as NiR(NR<SUP>1</SUP>R<SUP>2</SUP>)L<SUB>2</SUB>. A reaction of NiMe<SUB>2</SUB>(PEt<SUB>3</SUB>)<SUB>2</SUB> with CH<SUB>3</SUB>OH and phenyl isocyanate gives NiMe(N(Ph)COOMe)(PEt<SUB>3</SUB>)<SUB>2</SUB>. The IR, NMR, and visible spectroscopic studies of the complexes indicate that the electronegativity of Ni is enhanced by the replacement of one of the two R groups in <B>1</B> with the NR<SUP>1</SUP>R<SUP>2</SUP> ligand. NMR spectra of complexes of a type NiMe(NR<SUP>1</SUP>R<SUP>2</SUP>)(PEt<SUB>3</SUB>)<SUB>2</SUB> show that they have <I>trans</I>-configurations. Thermolyses of the monoalkylnickel(II) complexes start at temperatures higher by 80–100 °C than those of <B>1</B>, liberating RH, R–R, and olefin R(–H). Exposure of monoethylnickel(II) complexes to air releases ethylene as the main gaseous product. Reactions of the complexes of a type NiR(phthalimido)L<SUB>2</SUB> with R′X (R′=C<SUB>6</SUB>H<SUB>5</SUB>, C<SUB>6</SUB>H<SUB>5</SUB>CH<SUB>2</SUB>) and C<SUB>6</SUB>H<SUB>5</SUB>COCl produce <I>N</I>-alkyl- or <I>N</I>-arylphthalimide and ketone C<SUB>6</SUB>H<SUB>5</SUB>COR, respectively.
- 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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Kohara Teiji
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
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