The curious case of co-planarity in di-nuclear triel complexes: a density functional investigation†

IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR
Mayank Khera and Neetu Goel
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Abstract

Density functional investigation of intramolecular triel (Tr) bonding present in di-nuclear aryl complexes of group 13 elements having general formula [(Tr)Me2(2,6-(X)2C6H3O)]2 (Tr = B, Al, Ga, In & Tl and X = OMe, OEt, OH, OPh, NH2, SH, Cl, F) has been performed. Conclusive evidence of the concurrent two σ-hole interaction has been provided by analysis of the Tr bond length, interaction energy (ΔE), second order perturbation energy (E2), charge transfer (Δq), quantum theory of atom in molecules (QTAIM) and noncovalent interaction (NCI) plots for 12 complexes. The Tr bond length in the optimized geometry varies from 2.49 to 2.89 Å in Al complexes (1–8) and 2.66 to 2.83 Å in other group 13 element complexes (9–12) at the PBE0-D3 functional. The interaction energy calculation reveals that the co-planar structure of complexes containing Al (1–8) are more stable than their rotamers by 8–15 kcal mol−1, whereas the di-nuclear complexes of other group 13 complexes (9–12) orient in a non-planar pocket structure. This loss of co-planarity reveals the fact that its presence relies on the Tr atom, not the intramolecular Tr bonding, which has a striking impact on the crystal engineering of di-nuclear complexes of Group 13.

Abstract Image

双核三硒络合物共面性的奇特案例:密度函数研究
我们对通式为 [(Tr)Me2(2,6-(X)2C6H3O)]2(Tr = B、Al、Ga、In & Tl 和 X = OMe、OEt、OH、OPh、NH2、SH、Cl、F)的 13 族元素二核芳基配合物中存在的分子内三硒键(Tr)进行了密度泛函研究。通过分析 12 个复合物的 Tr 键长度、相互作用能 (ΔE)、二阶扰动能 (E2)、电荷转移 (Δq)、分子中原子的量子理论 (QTAIM) 和非共价相互作用 (NCI) 图,提供了同时存在两个 σ 孔相互作用的确凿证据。在 PBE0-D3 功能下,铝配合物(1-8)优化几何形状中的 Tr 键长度从 2.49 Å 到 2.89 Å 不等,其他 13 族元素配合物(9-12)的 Tr 键长度从 2.66 Å 到 2.83 Å 不等。相互作用能计算显示,含 Al 的配合物(1-8)的共平面结构比其转子结构稳定 8-15 kcal/mol,而其他 13 族元素的双核配合物(9-12)则以非平面口袋结构定向。这种共面性的丧失揭示了一个事实,即它的存在依赖于 Tr 原子,而不是分子内的 Tr 键,这对第 13 组双核配合物的晶体工程学产生了显著影响。
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来源期刊
Dalton Transactions
Dalton Transactions 化学-无机化学与核化学
CiteScore
6.60
自引率
7.50%
发文量
1832
审稿时长
1.5 months
期刊介绍: Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.
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