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首页> 美国卫生研究院文献>Chemical Science >Tris(1-isopropylbenzimidazol-2-yl)dimethylsilylmethyl metal complexes TismPriBenzM: a new class of metallacarbatranes isomerization to a tris(N-heterocyclic carbene) derivative and evidence for an inverted ligand field
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Tris(1-isopropylbenzimidazol-2-yl)dimethylsilylmethyl metal complexes TismPriBenzM: a new class of metallacarbatranes isomerization to a tris(N-heterocyclic carbene) derivative and evidence for an inverted ligand field

机译：Tris （1-异丙基苯并咪唑-2-基）二甲基甲硅烷基甲基金属配合物TismPriBenz M：一类新的金属碳杂环戊烷异构化为三（N-杂环卡宾）衍生物以及配体场反转的证据

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摘要

The tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl]methyl ligand, [TismPriBenz], has been employed to form carbatrane compounds of both the main group metals and transition metals, namely [TismPriBenz]Li, [TismPriBenz]MgMe, [TismPriBenz]Cu and [TismPriBenz]NiBr. In addition to the formation of atranes, a zinc compound that exhibits κ3-coordination, namely [κ3-TismPriBenz]ZnMe, has also been obtained. Furthermore, the [TismPriBenz] ligand may undergo a thermally induced rearrangement to afford a novel tripodal tris(N-heterocyclic carbene) variant, as shown by the conversion of [TismPriBenz]Cu to [κ4-C4-TismPriBenz*]Cu. The transannular M–C bond lengths in the atrane compounds are 0.19–0.32 Å longer than the sum of the respective covalent radii, which is consistent with a bonding description that features a formally zwitterionic component. Interestingly, computational studies demonstrate that the Cu–Catrane interactions in [TismPriBenz]Cu and [κ4-C4-TismPriBenz*]Cu are characterized by an “inverted ligand field”, in which the occupied antibonding orbitals are localized more on carbon than on copper.
机译：三[（1-异丙基苯并咪唑-2-基）二甲基甲硅烷基]甲基配体[Tism Pr i Benz ]已被用于形成两个主要基团的甲氧戊环化合物金属和过渡金属，例如[Tism Pr i Benz ] Li，[Tism Pr i Benz ] MgMe， [Tism Pr i Benz ] Cu和[Tism Pr i Benz ] NiBr。除形成芳烃外，锌化合物还表现出κ 3 -配位，即[κ 3 -Tism Pr i 还获得了苯并[Zn] ZnMe。此外，[Tism Pr i Benz ]配体可能会发生热诱导的重排，从而提供一个新颖的三脚架三（N-杂环卡宾）变体，如[Tism Pr i Benz ] Cu到[κ 4 -C4-Tism Pr i Benz ** ]铜。芳族化合物中跨环M–C键的长度比各自共价半径的总和长0.19–0.32Å，这与具有正式两性离子成分的键描述相一致。有趣的是，计算研究表明，[Tism Pr i Benz ] Cu和[κ 4 -C4-Tism 中的Cu-Catrane相互作用> Pr i Benz * ] Cu的特征是“倒配体场”，其中所占据的反键轨道更多地位于碳上而不是铜上。

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