Electronic structure and reactivity of mixed-ligand dinuclear RuIr, RuRh, and RuRu polyhydride-bridged complexes: A DFT-based investigation

IF 2.8 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron Pub Date : 2026-02-01 Epub Date: 2025-11-28 DOI:10.1016/j.poly.2025.117909

Abdelatif Messaoudi

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Abstract

This study presents a comprehensive theoretical analysis of a series of bimetallic diruthenium complexes [Cp^‡Ru(μ-H)₃IrCp^⁎], [Cp^‡Ru(μ-H)₃RhCp^⁎], [Cp^‡Ru (μ-H)₃{Ru(p-cymene)}], [Cp^‡Ru(μ-H)₃{Ru(benzene)}] and [Cp^‡Ru(μ-H)₂(μ-Cl){Ru(p-cymene)}] (Cp* = C₅Me₅, Cp^‡ = C5^tBu₃H₂, p-cymene = CH₃C₆H₄CH(CH₃)₂)) (A1-A5), incorporating various metal centers (Ir, Rh) and ligands (hydrides, chloride, Cp*) using density functional theory (DFT) at the B3LYP level with LanL2DZ and def2-TZVP basis sets. The geometric structures, electronic configurations, molecular orbitals, global reactivity descriptors, electrostatic potentials, atomic charges, TDOS, UV–Vis absorption spectra, and nonlinear optical (NLO) properties were systematically investigated. Geometry optimizations reveal excellent agreement with experimental data, with def2-TZVP offering slightly improved accuracy in metal-ligand bond distances and angles. The HOMO-LUMO gap analysis and frontier molecular orbitals show that complexes A1 and A5 have the narrowest gaps, indicating higher reactivity, while A3 displays the highest electron delocalization and charge transfer capability. Reactivity descriptors position A2 as the most electrophilic species, with high electronegativity and electron affinity, whereas A3 acts as the best donor. Molecular electrostatic potential (MESP) maps show distinct charge distributions and identify nucleophilic and electrophilic regions, highlighting the strong influence of ligand identity. Charge analysis supports significant polarization effects, particularly in A5 due to the chloride ligand. UV–Vis spectral simulations predict strong absorption in the visible region for A5, with metal to ligand charge transfer (MLCT) and π → π* transitions, indicating potential in photonic applications. Furthermore, NLO property analysis reveals that A3-A5 exhibit substantial hyperpolarizabilities, suggesting their promise as materials for second-order NLO applications. Altogether, this work underscores the sensitivity of electronic and optical properties to ligand environment, metal type, and computational treatment, offering valuable guidance for the design of functional organometallic complexes in catalysis, optoelectronics, and molecular electronics.

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混合配体双核RuIr、ruh和ruu多氢化物桥接配合物的电子结构和反应性：基于dft的研究

本研究利用密度泛函数理论（DFT）在B3LYP水平上结合了各种金属中心（Ir, Rh）和配体（氢化物，cl *），在LanL2DZ和def2-TZVP基集上，对一系列双金属钌配合物[Cp‡Ru(μ-H)3IrCp], [Cp‡Ru(μ-H)3{Ru(p-cymene)}], [Cp‡Ru(μ-H)3{Ru（苯）}]和[Cp‡Ru(μ-H)2(μ-Cl){Ru(p-cymene)} (Cp* = C5Me5, Cp‡= C5tBu3H2, p-cymene = CH3C6H4CH(CH3)2) （b1 - a5）进行了全面的理论分析。系统地研究了材料的几何结构、电子构型、分子轨道、整体反应性描述符、静电势、原子电荷、TDOS、紫外-可见吸收光谱和非线性光学性质。几何优化显示与实验数据非常吻合，def2-TZVP提供了金属配体键距离和角度的精度略有提高。HOMO-LUMO间隙分析和前沿分子轨道表明，配合物A1和A5的间隙最窄，反应活性较高，而A3的电子离域和电荷转移能力最强。反应性描述符表明A2是最亲电的物质，具有较高的电负性和电子亲和性，而A3是最好的供体。分子静电势（MESP）图显示出明显的电荷分布，并识别出亲核和亲电区域，突出了配体同一性的强烈影响。电荷分析支持显著的极化效应，特别是在A5中由于氯配体。紫外可见光谱模拟预测了A5在可见光区的强吸收，具有金属到配体的电荷转移（MLCT）和π→π*跃迁，表明其在光子领域的应用潜力。此外，NLO性质分析表明，A3-A5具有显著的超极化性，表明它们有望成为二阶NLO应用的材料。总之，这项工作强调了电子和光学性质对配体环境，金属类型和计算处理的敏感性，为催化，光电子和分子电子学中功能有机金属配合物的设计提供了有价值的指导。

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来源期刊

Polyhedron 化学-晶体学

CiteScore

4.90

自引率

7.70%

发文量

515

审稿时长

2 months

期刊介绍： Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry. Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.