硅z型配合物中共配体依赖的Rh(I) -Si （IV）相互作用

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-03-26 DOI:10.1021/acs.inorgchem.5c00368

Nils Ansmann, Jakob H. Alberts, Finn Hagen, Immanuel E. Blaum, Lutz Greb

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引用次数: 0

摘要

Rh(I) z型配合物具有σ-接受13基团路易斯酸，近年来已被证实在催化转化中是有效的。在这项工作中，我们报道了第一个Rh(I)硅烷z型配合物的分离和表征。由于Si（IV）具有较高的有效路易斯酸度，因此与它们的同类化合物相比，具有不同的性能，这导致了非常强的Rh(I) -Si （IV）键合。发现这种相互作用的性质高度依赖于Rh(I)上的配体的选择（例如，Cl, Me, Cp， H和CNCy）。通过实验技术和量子化学分析（NBO、QTAIM和ETS-NOCV）的结合，我们系统地研究了这种共配体依赖性。这些发现为设计和优化具有催化活性的Rh(I) z型配合物提供了有价值的见解。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Co-Ligand-Dependent Rh(I)–Si(IV) Interactions in Silicon Z-Type Complexes

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Co-Ligand-Dependent Rh(I)–Si(IV) Interactions in Silicon Z-Type Complexes

Rh(I) Z-type complexes featuring σ-accepting group 13 Lewis acids have been well established over recent years and proven efficient in catalytic transformations. In this work, we report the isolation and characterization of the first Rh(I) silane Z-type complexes. Distinct properties compared to their group 13 counterparts are exhibited due to the high effective Lewis acidity of Si(IV), which leads to remarkably strong Rh(I)–Si(IV) bonding. The nature of this interaction is found to be highly dependent on the choice of coligands at Rh(I) (e.g., Cl, Me, Cp, H, and CNCy). Through a combination of experimental techniques and quantum chemical analyses (NBO, QTAIM, and ETS-NOCV), we systematically investigate this coligand dependency. These findings provide valuable insights into the design and optimization of catalytically active Rh(I) Z-type complexes.

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.