Preparation and properties of monoalkylnickel(II) complexes having a phenoxo, benzenthiolato, oximato, .BETA.-diketonato, or halo ligand.
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概要
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Thirteen complexes of a type NiR(Y)L<I><SUB>n</SUB></I> (R=CH<SUB>3</SUB> (Me), C<SUB>2</SUB>H<SUB>5</SUB> (Et); Y=OC<SUB>6</SUB>H<SUB>5</SUB>, <I>p</I>-cyanophenoxo, 8-phenylphenoxo, 8-quinolinolato, OCOEt, OCOPh, acetophenone oximato, acetylacetonato, benzoylacetonato, Cl; L=trie thy lphosphine (PEt<SUB>3</SUB>), 2,2′-bipyridine (bpy)) have been prepared by reactions of dialkylnickel(II) complexes NiR<SUB>2</SUB>L<SUB>2</SUB> (<B>1</B>) with the corresponding active hydrogen compounds HY. Reactions of <B>1</B> with R′COY (Y=OC<SUB>6</SUB>H<SUB>5</SUB>, OCOC<SUB>6</SUB>H<SUB>5</SUB>, Cl) also afford the NiR(Y)L<I><SUB>n</SUB></I> type complexes with formation of unsymmetrical ketones RCOR′. Reactions of <B>1</B> with alcohols lead to dehydrogenation of alcohols to afford aldehydes or ketones. The NiR(Y)L<I><SUB>n</SUB></I> type complexes have been characterized by elemental analysis and spectroscopies (IR, NMR, visible). NMR spectra of <I>trans</I>-NiMe(OCOPh)(PEt<SUB>3</SUB>)<SUB>2</SUB>, NiMe(acetophenone oximato)(PEt<SUB>3</SUB>) (<B>11</B>), NiMe(benzoylacetonato) (PEt<SUB>3</SUB>) show temperature dependence, indicating occurrence of rapid dynamic reactions on NMR time scale in these complexes. The acetophenone oximato ligand in <B>11</B> is proposed to serve as an oxa-, aza-π-allylic ligand on the bases of IR and NMR spectroscopies. NiEt(OCOC<SUB>2</SUB>H<SUB>5</SUB>)(bpy) (<B>8</B>), NiEt(OCOC<SUB>6</SUB>H<SUB>5</SUB>)(bpy), and NiEt(Cl)(bpy) (<B>14</B>) undergo disproportionation reaction to give NiEt<SUB>2</SUB>(bpy) and NiY<SUB>2</SUB>(bpy) type complexes. Diethyl ketone is also produced during the disproportionation of <B>8</B>. Reactions of <B>14</B> with olefins having electron-withdrawing substituents afford NiCl<SUB>2</SUB>(bpy) and Ni(olefin)<SUB>2</SUB>(bpy).
- 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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