通过有效碎片轨道对联体的捐赠者-接受者特性的量化
Gerard Comas-Vilà1, Pedro Salvador1
1Departament de Química and Institut de Química Computacional i Catàlisi (IQCC), Universitat de Girona, Campus Montilivi s/n, 17071, Girona, Spain.
概括
本研究介绍了有效的碎片轨道 (EFO) 来量化金属-联体相互作用,详细介绍了西格玛捐赠和pi回捐赠. 旋转状态显著影响过渡金属复合体中的这些捐赠者-接受者特征.
科学领域:
- 无机化学 无机化学 有机化学
- 计算化学计算化学
- 量子化学 是一个量子化学.
背景情况:
- 金属-联体相互作用是过渡金属复合物的基础.
- 德沃-查特-肯森模型描述了通过电子捐赠和反捐赠的结合.
- 量化这些单独的捐赠和反捐赠效应在计算上具有挑战性.
研究的目的:
- 介绍一种用于识别和量化金属-连接体和供体-受体相互作用的一般计算程序.
- 为了引入新描述符的西格玛-捐赠者 (σd),pi-捐赠者 (πd),和pi-接受者 (πa) 字符.
- 分析金属特性和连接物多样性对这些相互作用的影响.
主要方法:
- 使用有效碎片轨道 (EFO) 和它们的职业.
- 开发了一种超出科恩-沙姆密度函数理论 (KS-DFT) 的方法.
- 将框架应用于具有多种连接体的Fe(II) 八面体复合体.
主要成果:
- 成功量化了各种配体的σ-捐赠者,π-捐赠者和π-接受者特征.
- 确定金属自旋状态是影响捐赠和反捐赠的最关键因素.
- 证明了 EFO 合理化既定参数的能力,如托尔曼电子参数和转移影响.
结论:
- 有效的碎片轨道提供了一种强大的方法来剖析金属-连接体结合.
- 旋转状态在调节金属和体之间的电子通信中起着至关重要的作用.
- 新的描述器提供了有关联体电子特性和复杂反应性的宝贵见解.
相关概念视频
02:58Crystal Field Theory - Octahedral Complexes
26.3K
Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
26.3K
02:51Metal-Ligand Bonds
20.7K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
20.7K
02:35Molecular Orbital Theory I
32.0K
Overview of Molecular Orbital Theory
32.0K
02:40MO Theory and Covalent Bonding
10.5K
The molecular orbital theory describes the distribution of electrons in molecules in a manner similar to the distribution of electrons in atomic orbitals. The region of space in which a valence electron in a molecule is likely to be found is called a molecular orbital. Mathematically, the linear combination of atomic orbitals (LCAO) generates molecular orbitals. Combinations of in-phase atomic orbital wave functions result in regions with a high probability of electron density, while...
10.5K
03:51Molecular Orbital Theory II
19.1K
Molecular Orbital Energy Diagrams
19.1K
01:18π Molecular Orbitals of the Allyl Cation and Anion
4.2K
An allyl group is a three-carbon conjugated system where the sp³-hybridized allylic carbon is bonded to a CH=CH2 group via a single bond. Allyl anions can be obtained by treating propene with a strong base that can deprotonate methyl groups. Allyl cations are formed as intermediates during substitution reactions involving allylic halides. In both cases, the hybridization of the allylic carbon changes from sp3 to sp2, giving rise to a carbon chain with three sp2-hybridized carbons, each with...
4.2K