Synthesis, Characterization, and Catalytic Activity of Ni(II) Alkyl Complexes Supported by Pyrrole-Diphosphine Ligands.
Synthesis, Characterization, and Catalytic Activity of Ni(II) Alkyl Complexes Supported by Pyrrole-Diphosphine Ligands.
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吡咯 - 二膦配体支持的Ni（II）烷基复合物的合成，表征和催化活性。
DOI：
10.1021/om400630q
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发表时间：
2013-08-26
期刊：
影响因子：
2.8
通讯作者：
Tonzetich ZJ
中科院分区：
文献类型：
--
作者：
Venkanna GT;Tammineni S;Arman HD;Tonzetich ZJ
报道了吡咯型钳形配体(P2RPYR)−(P2RPYR=2，5-(R2PCH2)2C4H2N，R=Ph或Cy)的金属有机镍化学。Grignard试剂与[NiCl(P2R PYR)]反应生成了各种烷基和芳基配合物(甲基、乙基、苯基、苯基和烯丙基)，它们都呈现出关于镍的正方形平面几何形状。氢化物配合物[NIH(P2 CyPyr)]也可以通过LiHBEt3处理[NiCl(P2 CyPyr)]或通过H(P2 RPyr)与[Ni(COD)2](COD=1，4-环辛二烯)反应而制备。甲基和氢化物分别与CO和CO2反应，表明Ni-C和Ni-H键发生了干净的迁移插入化学。在室温下，烷基和氯络合物都是芳基氯化物与芳基或烷基格氏试剂Kumada偶联的活性催化剂。报道了其中几个配合物的固态结构。
The organometallic Ni(II) chemistry of the pyrrole-based pincer ligands, (P2 RPyr)− (P2 RPyr = 2,5-(R2PCH2)2C4H2N, R = Ph or Cy) is reported. Reactions of Grignard reagents with [NiCl(P2R Pyr)] afford a variety of alkyl and aryl complexes (methyl, ethyl, benzyl, phenyl, and allyl) that all display square planar geometries about nickel. The hydride complex, [NiH(P2 CyPyr)], can also prepared either through treatment of [NiCl(P2 CyPyr)] with LiHBEt3, or by reaction of H(P2 RPyr) with [Ni(COD)2] (COD = 1,4-cyclooctadiene). Reactions of the methyl and hydride complexes with CO and CO2, respectively, evince clean migratory insertion chemistry of the Ni-C and Ni-H bonds. Both the alkyl and chloride complexes are active catalysts for the Kumada coupling of aryl chlorides and aryl or alkyl Grignard reagents at room temperature. The solid-state structures of several of the complexes are reported.
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