物理吸附分子催化剂的择优取向及其选择性意义。

IF 3.7 Q2 CHEMISTRY, PHYSICAL
ACS Physical Chemistry Au Pub Date : 2025-03-07 eCollection Date: 2025-05-28 DOI:10.1021/acsphyschemau.5c00007
Guillaume P Laurent, Samuel L Leonard, Mita Halder, Damien B Culver, Peng Xu, Mark S Gordon, Frédéric A Perras
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引用次数: 0

摘要

立体选择性催化中的约束效应一直是人们长期研究的课题。结果在很大程度上是混杂的,有报道称限制既提高了选择性又降低了选择性。我们理解表面对催化机制的影响的能力,因此,选择性,已经严重阻碍了在支撑金属配合物的结构中常见的低水平的细节。灵敏度增强核磁共振的最新发展不仅揭示了表面位点的分子结构,而且揭示了它们的构型、取向和邻近分子的接近度。在研究[Rh-(环二烯)-((S)-(S)-(-)-2-氨基甲基-1-乙基吡咯烷)]- cf3so3非共价固定于二氧化硅(一种对映选择性加氢催化剂)上时,我们观察到相对于载体表面,配合物对特定取向有很强的偏好。我们讨论了优先吸附如何有助于减少竞争反应途径的数量,进而对选择性产生巨大影响。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Preferred Orientation of a Physisorbed Molecular Catalyst and Implications for Selectivity.

Confinement effects in stereoselective catalysis have been the topic of prolonged inquiry. Results have been largely mixed, with confinement having been reported to both enhance and degrade selectivity. Our ability to understand the surface's impact on catalytic mechanisms, and thus selectivity, has been severely hindered by the low level of details commonly seen in the structures of supported metal complexes. Recent developments in sensitivity-enhanced NMR are revealing not only the molecular structure of surface sites but also their configuration, orientation, and proximities to neighboring molecules. In studying [Rh-(cyclooctadiene)-((S)-(-)-2-aminomethyl-1-ethyl-pyrrolidine)]-CF3SO3 noncovalently immobilized to silica, an enantioselective hydrogenation catalyst, we observed a strong preference for a particular orientation of the complex relative to the support surface. We discuss how preferential adsorption may help reduce the number of competing reaction pathways and, in turn, have outsized effects on selectivity.

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来源期刊
CiteScore
3.70
自引率
0.00%
发文量
0
期刊介绍: ACS Physical Chemistry Au is an open access journal which publishes original fundamental and applied research on all aspects of physical chemistry. The journal publishes new and original experimental computational and theoretical research of interest to physical chemists biophysical chemists chemical physicists physicists material scientists and engineers. An essential criterion for acceptance is that the manuscript provides new physical insight or develops new tools and methods of general interest. Some major topical areas include:Molecules Clusters and Aerosols; Biophysics Biomaterials Liquids and Soft Matter; Energy Materials and Catalysis
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