σ-Aromatic Envelope Geometry in Penta Coordinated Group 13-Bridged Transition Metal Carbonyl Clusters

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry Pub Date : 2025-10-04 DOI:10.1016/j.comptc.2025.115531

Chhanda Paul, Sumit Satish Kadam, Shanti Gopal Patra

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Abstract

In this study, five-membered ring containing penta-coordinated group 13 metal carbonyl clusters of the type [(μ-E){M(CO)₄}₅]²⁻, where E = B, Al, Ga, In, and M = Mn, Tc, Re are considered. DFT was employed for geometry optimization, revealing unusual but stable envelope-like structures, while aromatic character was evaluated using magnetic criteria, including Nucleus Independent Chemical Shifts (NICS), Gauge-Including Magnetically Induced Currents (GIMIC), etc. All the carbonyl clusters show σ-aromaticity. These studies reveal notable diatropic ring currents and highly negative NICS values in selected clusters of [(μ-E){M(CO)₄}₅]²⁻ species, indicative of strong σ-aromaticity. The σ-aromaticity is confirmed by NICS scan, NICS decomposition, and Natural Orbitals for Chemical Valence (NOCV). The trends in aromaticity are NICS: B > Al > Ga > In (Mn), and B > In ≥ Ga > Al (Tc, Re); GIMIC: B > Ga > In > Al (Mn), and B > In ≥ Ga > Al (Tc, Re).

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五配位基团13-桥接过渡金属羰基团簇的σ-芳香包络几何

本文考虑了[(μ-E){M(CO)4}5]2−型的含五配位基团13个金属羰基簇的五元环，其中E = B, Al, Ga, In, M = Mn, Tc, Re。采用离散傅里叶变换（DFT）进行几何优化，揭示了不寻常但稳定的包络状结构，并利用核独立化学位移（NICS）、含规磁感应电流（GIMIC）等磁准则评价了芳香特性。所有羰基簇均表现出σ-芳香性。这些研究表明，在[(μ-E){M(CO)4}5]2−种簇中存在显著的各向异性环电流和高度负的NICS值，表明它们具有较强的σ-芳香性。通过NICS扫描、NICS分解和化学价态自然轨道（NOCV）验证了其σ-芳构性。芳香性的趋势是NICS: B >； Al > Ga > in （Mn）和B >； in≥Ga > Al (Tc, Re)；GIMIC: B在Ga祝辞的祝辞Al (Mn)和B祝辞在≥Ga在Al (Tc, Re)。

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来源期刊

Computational and Theoretical Chemistry CHEMISTRY, PHYSICAL-

CiteScore

4.20

自引率

10.70%

发文量

331

审稿时长

31 days

期刊介绍： Computational and Theoretical Chemistry publishes high quality, original reports of significance in computational and theoretical chemistry including those that deal with problems of structure, properties, energetics, weak interactions, reaction mechanisms, catalysis, and reaction rates involving atoms, molecules, clusters, surfaces, and bulk matter.