A four-parameter system for rationalising the electronic properties of transition metal-radical ligand complexes.,Dalton Transactions

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A four-parameter system for rationalising the electronic properties of transition metal-radical ligand complexes.
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-06-29 , DOI: 10.1039/d0dt02237c
N M Mews ₁ , M Reimann ₂ , G Hörner ₃ , M Kaupp ₂ , H Schubert ₁ , A Berkefeld ₁

Affiliation

A system of four principal parameters is reported that provides a unified description of the electronic and chemical properties of radical-ligand coordination compounds. This type of parametrisation applies to compositionally different types of radical-ligands, and the principal parameters rank in the following order: (a) coordination mode (metal–ligand orbital alignment) > (b) metal linkage > (c) ligand charge > (d) geometric strain (on orbital overlap). A series of group-10 metal complexes of an open-shell thiolate-arene-thiolate ligand suits to differentiate between three of the four effects in a clear-cut fashion, which allowed sorting these into a semi-quantitative order for the first time. Combined experimental and TD-DFT data aided in distinguishing structural effects from metal specific contributions such as relativistic effects. The applicability of spectroscopic and structure properties to serve as characteristic markers for comparison is discussed with regard to the large body of planar radical-ligand structures.

中文翻译：

四参数系统，用于合理化过渡金属-自由基配体配合物的电子性质。

据报道，由四个主要参数组成的系统可提供对自由基-配体配位化合物的电子和化学性质的统一描述。这种类型的参数化适用于组成不同类型的自由基-配体，主要参数按以下顺序排列：（a）配位模式（金属-配体轨道排列）>（b）金属键>（c）配体电荷>（ d）几何应变（在轨道重叠处）。开壳硫醇盐-芳烃-硫醇盐配体的一系列第10组金属络合物适合以清晰的方式区分四种效应中的三种，从而首次将它们分类为半定量顺序。结合实验数据和TD-DFT数据有助于区分结构效应和金属特定贡献（如相对论效应）。

更新日期：2020-07-21

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