Autocatalytic Activation of a Ruthenium-PNN-Pincer Hydrogenation Catalyst

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2024-10-23 DOI:10.1021/acscatal.4c0447510.1021/acscatal.4c04475

Jose Fernando Carbajal Perez, Fallyn L. Kirlin, Eamon F. Reynolds, Cole E. Altomare-Jarczyk, Benjamin T. Joseph, Jason M. Keith* and Anthony R. Chianese*,

引用次数: 0

Abstract

In this article, we describe a detailed experimental and computational study of the activation mechanism for a highly active pincer ruthenium(0) precatalyst for the hydrogenation of polar organic compounds. The precatalyst activates by reaction with 2 equiv of hydrogen, resulting in a net oxidative addition to ruthenium and hydrogenation of an imine functional group on the supporting ligand. The kinetics of precatalyst hydrogenation were measured by UV–visible spectroscopy under catalytically relevant conditions (10–39 bar hydrogen, 298 K). The kinetic data, in combination with density functional theory calculations, support an intriguing autocatalytic mechanism, where the product ruthenium(II) complex catalyzes the hydrogenation of the ruthenium(0) precatalyst.

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钌-PNN-钳形氢化催化剂的自动催化活化

在这篇文章中，我们描述了对极性有机化合物氢化过程中高活性钳形钌（0）前催化剂活化机理的详细实验和计算研究。该前催化剂通过与 2 等量的氢发生反应而活化，从而导致钌的净氧化加成和支持配体上一个亚胺官能团的氢化。在催化相关条件（10-39 巴氢气，298 K）下，通过紫外可见光谱测量了前催化剂氢化的动力学。动力学数据与密度泛函理论计算相结合，支持一种有趣的自催化机制，即产物钌（II）复合物催化钌（0）前催化剂的氢化反应。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.