Reactions of dialkylnickel(II) complexes NiR2L2 with alkyl (or aryl) halides, R'COY (Y=Cl,Br,OPh,OCOPh), and CS2.
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Reactions of Ni(CH<SUB>3</SUB>)<SUB>2</SUB>(bpy) (<B>1</B>), Ni(C<SUB>2</SUB>H<SUB>5</SUB>)<SUB>2</SUB>(bpy) (<B>2</B>) (bpy=2,2′-bipyridine), <I>trans</I>-Ni(CH<SUB>3</SUB>)<SUB>2</SUB>(triethylphosphine)<SUB>2</SUB> (<B>3</B>), Ni(CH<SUB>3</SUB>)<SUB>2</SUB>(1,2-bis(diphenylphosphino)ethane) (<B>4</B>), and Ni(CH<SUB>3</SUB>)<SUB>2</SUB>(1,3-bis(diphenylphosphino)propane) (<B>5</B>) with alkyl or aryl halides, R′COY (Y=Cl, Br, OC<SUB>6</SUB>H<SUB>5</SUB>, OCOC<SUB>6</SUB>H<SUB>5</SUB>), and CS<SUB>2</SUB> have been investigated. The reactions of NiR<SUB>2</SUB>L<SUB>2</SUB> with alkyl or aryl halides are classified into three types of reactions by their reactirn products: Type A: NiR<SUB>2</SUB>L<SUB>2</SUB>+R′X→NiX(R′)L<SUB>2</SUB>+R–R, Type B: NiR<SUB>2</SUB>L<SUB>2</SUB>+R′X→alkane (RH)+ olefin (R′(–H)), and Type C: NiR<SUB>2</SUB>L<SUB>2</SUB>+R′X→NiR(X)L<SUB>2</SUB>+R–R′. Complexes <B>1</B> and <B>2</B> undergo mainly Type A reaction. Complex <B>3</B> gives Type A reaction product on treatment with C<SUB>6</SUB>H<SUB>5</SUB>Br, but it gives Type B reaction product on treatment with C<SUB>2</SUB>H<SUB>5</SUB>Br. On the other hand, <B>4</B> undergoes Type C reaction on interaction with C<SUB>6</SUB>H<SUB>5</SUB>Cl. The reactions with R′COY (Y=Cl, Br, OPh, OCOPh) are classified into two types of reactions by their reaction products: Type D: NiR<SUB>2</SUB>L<SUB>2</SUB>+R′COY→NiY(R′)L<SUB>2</SUB>+RCOR′ and Type E: NiR<SUB>2</SUB>L<SUB>2</SUB>+R′COY→NiY(R′)L<SUB>2</SUB>+RCOR. Complexes <B>1</B>–<B>3</B> undergo mainly Type D reaction, whereas complexes <B>4</B> and <B>5</B> mainly Type E reaction. The difference in the reaction route is discussed on the basis of presence or absence of vacant coordination site for attack by R′COY. The reaction of <B>4</B> with CS<SUB>2</SUB> affords Ni(CS<SUB>2</SUB>)(1,2-bis(diphenylphosphino)ethane) with evolution of a reductive elimination product, ethane, whereas the reaction of <B>3</B> with CS<SUB>2</SUB> gives a 1:1 adduct of <B>3</B> and CS<SUB>2</SUB>.
- 公益社団法人 日本化学会の論文
著者
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Osakada Kohtaro
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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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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