A Nickel Complex Containing a Pyramidalized, Ambiphilic Pincer Germylene Ligand.,Chemistry - A European Journal

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A Nickel Complex Containing a Pyramidalized, Ambiphilic Pincer Germylene Ligand.
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2019-09-30 , DOI: 10.1002/chem.201903069
Takahito Watanabe ₁ , Yumi Kasai ₁ , Hiromi Tobita ₁

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Reaction of N-heterocyclic carbene (NHC)-stabilized PGeP-type germylene Ge{o-(PiPr2 )C6 H4 }2 ⋅Me IiPr (1) (Me IiPr=1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) with Ni(cod)2 gave pincer germylene complex Ni[Ge{o-(PiPr2 )C6 H4 }2 ](Me IiPr) (2), in which the Ge center of 2 is significantly pyramidalized. Theoretical calculation on 2 predicted the ambiphilicity of the germanium center, which was confirmed by reactivity studies. Thus, complex 2 reacted with both Lewis base Me IMe (Me IMe=1,3,4,5-tetramethylimidazol-2-ylidene) and Lewis acid BH3 ⋅SMe2 at the germanium center to afford the adducts Ni[Ge{o-(PiPr2 )C6 H4 }2 ⋅Me IMe](Me IiPr) (3) and Ni[Ge{o-(PiPr2 )C6 H4 }2 ⋅BH3 ](Me IiPr) (4), respectively. Furthermore, the former was slowly converted to dinuclear complex Ni2 [Ge{o-(PiPr2 )C6 H4 }2 ]2 (Me IMe)2 (5) at room temperature. Complex 5 can be regarded as a dimer of the Me IMe analog of 2 with a Ni-Ge-Ge-Ni linkage.

中文翻译：

含金字塔形，两亲夹钳的二甲苯锗配体的镍配合物。

N杂环卡宾（NHC）稳定的PGeP型亚甲基Ge {o-（PiPr2）C6 H4} 2⋅MeIiPr（1）（Me IiPr = 1,3-二异丙基-4,5-二甲基咪唑-2-亚叉基）与Ni（cod）2生成夹钳的亚ylene基络合物Ni [Ge {o-（PiPr2）C6 H4} 2]（Me IiPr）（2），其中2的Ge中心显着呈锥体状。对2的理论计算预测了锗中心的歧义性，这已通过反应性研究得到了证实。因此，配合物2与路易斯碱Me IMe（Me IMe = 1,3,4,5-四甲基咪唑-2-亚基）和路易斯酸BH3⋅SMe2在锗中心反应，得到加合物Ni [Ge {o-（ PiPr2）C6 H4} 2⋅MeIMe]（Me IiPr）（3）和Ni [Ge {o-（PiPr2）C6 H4} 2⋅BH3]（Me IiPr）（4）。此外，前者在室温下缓慢转化为双核络合物Ni2 [Ge {o-（PiPr2）C6 H4} 2] 2（Me IMe）2（5）。

更新日期：2019-09-30

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