A Nickel Complex Containing a Pyramidalized, Ambiphilic Pincer Germylene Ligand
A Nickel Complex Containing a Pyramidalized, Ambiphilic Pincer Germylene Ligand
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含有金字塔化、两亲性钳甲亚甲配体的镍络合物
DOI：
10.1002/chem.201903069
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
and H. Tobita
中科院分区：
文献类型：
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作者：
T. Watanabe;Y. Kasai;and H. Tobita
N -杂环碳（NHC）稳定的PGeP型germylene Ge{o‐（PiPr2）C6H4}2·MeIiPr (1) （MeIiPr=1,3‐二异丙基‐4,5‐二甲基咪唑‐2‐基）与Ni(cod)2反应得到钳形germylene配合物Ni[Ge{o‐（PiPr2）C6H4}2](MeIiPr)(2)，其中2的Ge中心明显锥体化。理论计算预测了锗中心的双亲性，反应性研究证实了这一点。因此，配合物2在锗中心与Lewis碱emeime （meme =1,3,4,5‐四甲基咪唑‐2‐基二烯）和Lewis酸BH3⋅sme2反应，分别生成Ni[Ge{o‐（PiPr2）C6H4}2⋅meme](MeIiPr)(3)和Ni[Ge{o‐（PiPr2）C6H4}2⋅BH3](MeIiPr)(4)。此外，前者在室温下缓慢转化为双核配合物Ni2[Ge{o‐（PiPr2）C6H4}2]2(meme)2(5)。络合物5可以看作是具有Ni - Ge - Ge - Ni键的2的meme类似物的二聚体。
Reaction of N‐heterocyclic carbene (NHC)‐stabilized PGeP‐type germylene Ge{o‐(PiPr2)C6H4}2⋅MeIiPr (1) (MeIiPr=1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) with Ni(cod)2gave pincer germylene complex Ni[Ge{o‐(PiPr2)C6H4}2](MeIiPr) (2), in which the Ge center of2is significantly pyramidalized. Theoretical calculation on2predicted the ambiphilicity of the germanium center, which was confirmed by reactivity studies. Thus, complex2reacted with both Lewis baseMeIMe (MeIMe=1,3,4,5‐tetramethylimidazol‐2‐ylidene) and Lewis acid BH3⋅SMe2at the germanium center to afford the adducts Ni[Ge{o‐(PiPr2)C6H4}2⋅MeIMe](MeIiPr) (3) and Ni[Ge{o‐(PiPr2)C6H4}2⋅BH3](MeIiPr) (4), respectively. Furthermore, the former was slowly converted to dinuclear complex Ni2[Ge{o‐(PiPr2)C6H4}2]2(MeIMe)2(5) at room temperature. Complex5can be regarded as a dimer of theMeIMe analog of2with a Ni‐Ge‐Ge‐Ni linkage.