碱性和亲核性在alh3碱加合物电荷转移中的作用:理论研究

Mohammed Aichi, Meriem Hafied
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引用次数: 0

摘要

本研究允许探索路易斯酸(AlH3)和路易斯碱:CO;水;氨;PH3;PC13;硫化氢;CN -;哦- - - - - -;O2-2;F -;N (CH3) 3;氮气;N2H4;N2H2;C5H5N;C6H5-NH2。采用6-31G(d,p)基集,利用B3LYP泛函数进行DFT理论计算,为了检验供体和受体对不同加合物的建立的影响,我们主要计算了alh3碱的能差∆EHOMO-LUMO、吉布斯能∆G、角(θ)和相互作用能Einter。通过计算反应性的几个参数(亲电性指数(ω)、亲核性(N)、化学势(μ)、硬度(η)和极化率(α))来定义弱相互作用,并区分不同路易斯碱的亲核性和碱性。结果表明,在Al和阴离子碱之间建立相互作用的体系中,估计电子电荷转移是重要的,并且可以预测O-2, F -, OH -和CN -的电子供体功率。伪四面体加合物的排列取决于参数几何(键长、相互作用和θ角)和表征主稳定性的吉布斯能∆G。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Basicity and Nucleophilicity Effect in Charge Transfer of AlH3-Base Adducts: Theoretical Approach
This study permits to explore the interactions involved in Lewis acid (AlH3) and Lewis bases: CO; H2O; NH3; PH3; PC13; H2S; CN–; OH–; O2–2; F–; N(CH3)3; N2; N2H4; N2H2; C5H5N; C6H5-NH2. By means of DFT theory calculations with B3LYP functional using 6-31G(d,p) basis set and in order to check the effects of both the donor and the acceptor in the establishment of the different adducts we focused mainly on the calculation of the energetic gap ∆EHOMO-LUMO, Gibbs energies ∆G, the angle (θ) in AlH3-base and the interaction energy values Einter. The several parameters of the reactivity (electrophilicity index (ω), nucleophilicity (N), chemical potential (μ), hardness (η), and polarizability (α)) are also calculated to define the weak interaction as well as to distinguish between the nucleophilicity and basicity of different Lewis bases. The results showed that the electronic charge transfer is estimated to be important in the systems where the interaction is established between Al and anionic bases, and the electron donor power is predictable for O–2, F–, OH–, and CN–. The pseudo-tetrahedral adduct arrangements depend on the parameter geometries (bond length interaction and θ angle) and Gibbs energies ∆G characterizing the main stability.
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