低价 14 族络合物激活 CO 2 的非共价相互作用和电荷转移。

IF 2.1 4区 化学 Q4 BIOCHEMISTRY & MOLECULAR BIOLOGY
Carlos Castillo-Orellana, Esteban Vöhringer-Martinez, Nery Villegas-Escobar
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引用次数: 0

摘要

背景:低价 14 族催化剂对 CO 2 的活化作用包括在单一过渡态中通过协同途径断裂各种共价键。中央主基团原子与络合物中氢化物之间的键被拉长,从而引发与 CO 2 形成 C-H 键,同时络合物与 CO 2 之间形成 E-O 键,从而产生相应的甲酸酯产物。先前的研究已经证实,除了 CO 2 的无极性之外,它与复合物的初始相互作用主要受静电作用的支配。值得注意的是,我们忽略了反应初始阶段催化剂与 CO 2 之间的其他稳定作用和电荷转移。在本研究中,我们对促进第 14 组主基团复合物活化 CO 2 的非共价相互作用和电荷转移进行了量化。我们的研究结果表明,静电相互作用主要稳定了反应物区域的络合物和 CO 2。然而,随着反应向过渡态发展,感应能超越静电作用,成为主要的稳定力量。感应能对过渡态的稳定作用约占 50%,其次是静电(40%)和分散相互作用(10%)。用最小基迭代持股法(MBIS)计算的原子电荷显示,在 CO 2 接近催化剂的背面反应路径中,电荷转移比正面反应路径大。值得注意的是,我们发现 CO 2 稍微弯曲至约 176 ∘ 的初始位置会启动所有体系的电荷转移过程。此外,我们对 14 族元素的研究表明,当 14 族元素下降时,活化能和向 CO 2 的电荷转移都会系统地降低:方法:所有研究的反应都是根据 M06-2X/6-31 g(d,p) 理论水平的本征反应坐标(IRC)方法得到的反应坐标进行表征的。使用 DLPNO-CCSD(T)/cc-pVTZ-SSD(E)理论水平的电子能量计算了甲苯中的吉布斯自由能。为了更准确地描述得到的吉布斯自由能,还应用了振动和平移熵修正。为了更好地描述所有反应的反应坐标变化,采用了反应力分析(RFA)。它可以将反应坐标划分为反应物区域、过渡态区域和产物区域,在这些区域中会出现机理的不同阶段。利用对称适应扰动理论(SAPT)详细分析了低价 14 族配合物活化 CO 2 初始阶段的主要非共价驱动力。这些计算采用了 SAPT0-CT/def2-SVP 方法。此外,还利用 MBIS 方案获得了基于原子群的电荷转移描述符,以补充 SAPT 分析。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Non-covalent interactions and charge transfer in the CO\(_{2}\) activation by low-valent group 14 complexes

Context

The CO\(_{2}\) activation by low-valent group 14 catalysts encompasses the rupture of varied covalent bonds in a single transition state through a concerted pathway. The bond between the central main group atom and the hydride in the complex is elongated to trigger the formation of the C–H bond with CO\(_{2}\) accompanied by the concomitant formation of the E–O bond between the complex and CO\(_{2}\) to lead the corresponding formate product. Prior studies have established that besides the apolar nature of CO\(_{2}\), its initial interaction with the complex is primarily governed by electrostatic interactions. Notably, other stabilizing interactions and the transfer of charge between catalysts and CO\(_{2}\) during the initial phases of the reaction have been ignored. In this study, we have quantified the non-covalent interactions and charge transfer that facilitate the activation of CO\(_{2}\) by group 14 main group complex. Our findings indicate that electrostatic interactions predominantly stabilize the complex and CO\(_{2}\) in the reactant region. However, induction energy becomes the main stabilizing force as the reaction progresses towards the transition state, surpassing electrostatics. Induction contributes about 50% to the stabilization at the transition state, followed by electrostatics (40%) and dispersion interactions (10%). Atomic charges calculated with the minimal basis iterative stockholder (MBIS) method reveal larger charge transfer for the back-side reaction path in which CO\(_{2}\) approaches the catalysts in contrast to the front-side approach. Notably, it was discovered that a minor initial bending of CO\(_{2}\) to approximately \(176^\circ \) initiates the charge transfer process for all systems. Furthermore, our investigation of group 14 elements demonstrates a systematic reduction in both activation energies and charge transfer to CO\(_{2}\) while descending in group 14.

Methods

All studied reactions were characterized along the reaction coordinate obtained with the intrinsic reaction coordinate (IRC) methodology at the M06-2X/6-31 g(d,p) level of theory. Gibbs free energy in toluene was computed using electronic energies at the DLPNO-CCSD(T)/cc-pVTZ-SSD(E) level of theory. Vibrational and translational entropy corrections were applied to provide a more accurate description of the obtained Gibbs free energies. To better characterize the changes in the reaction coordinate for all reactions, the reaction force analysis (RFA) has been employed. It enables the partition of the reaction coordinate into the reactant, transition state, and product regions where different stages of the mechanism occur. A detailed characterization of the main non-covalent driving forces in the initial stages of the activation of CO\(_{2}\) by low-valent group 14 complexes was performed using symmetry-adapted perturbation theory (SAPT). The SAPT0-CT/def2-SVP method was employed for these computations. Charge transfer descriptors based on atomic population using the MBIS scheme were also obtained to complement the SAPT analyses.

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来源期刊
Journal of Molecular Modeling
Journal of Molecular Modeling 化学-化学综合
CiteScore
3.50
自引率
4.50%
发文量
362
审稿时长
2.9 months
期刊介绍: The Journal of Molecular Modeling focuses on "hardcore" modeling, publishing high-quality research and reports. Founded in 1995 as a purely electronic journal, it has adapted its format to include a full-color print edition, and adjusted its aims and scope fit the fast-changing field of molecular modeling, with a particular focus on three-dimensional modeling. Today, the journal covers all aspects of molecular modeling including life science modeling; materials modeling; new methods; and computational chemistry. Topics include computer-aided molecular design; rational drug design, de novo ligand design, receptor modeling and docking; cheminformatics, data analysis, visualization and mining; computational medicinal chemistry; homology modeling; simulation of peptides, DNA and other biopolymers; quantitative structure-activity relationships (QSAR) and ADME-modeling; modeling of biological reaction mechanisms; and combined experimental and computational studies in which calculations play a major role.
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