在与胺的CO2还原偶联反应中，阳离子铟配合物使H2分压减半

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis Pub Date : 2025-09-18 DOI:10.1016/j.jcat.2025.116445

Pritha Saha , Martin Zábranský , Laura E. English , Andrew R. Jupp , Martin Hulla

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引用次数: 0

摘要

铟催化的均相加氢仅限于亚胺加氢，因为In(C6F5)3的热和水解稳定性较低，In(C6F5)3是迄今为止唯一用于加氢化学的铟刘易斯酸。在这项研究中，我们提出了[In(terpy)Cl2]+阳离子作为刘易斯酸催化剂。在H2（50 bar）和CO2（4 bar）压力下，[In(terpy)Cl2]+在H2（50 bar）和CO2（4 bar）压力下有效催化了CO2与胺的还原偶联，具有H2活化的最佳空位和高达579 kJ mol−1的氢化物离子亲和力，XRD和NMR结构证实了这一点。通过在所有其他主基团催化体系的一半分压下与H2催化CO2与胺的还原偶联，阳离子铟配合物为此类反应设定了新的基准。因此，本研究不仅扩大了铟基催化亚胺加氢的范围，而且突出了配体负载的铟路易斯酸作为小分子活化催化体系的潜力

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Cationic indium complexes halve H2 partial pressure in CO2 reductive coupling reactions with amines

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Cationic indium complexes halve H2 partial pressure in CO2 reductive coupling reactions with amines

Indium-catalysed homogeneous hydrogenations are limited to imine hydrogenation due to the low thermal and hydrolytic stability of In(C₆F₅)₃, the only indium Lewis acid used thus far for hydrogenation chemistry. In this study, we present [In(terpy)Cl₂]⁺ cations as Lewis acid catalysts. With an optimal vacant site for H₂ activation and a hydride ion affinity of up to 579 kJ mol⁻¹, [In(terpy)Cl₂]⁺ effectively catalysed CO₂ reductive coupling with amines under H₂ (50 bar) and CO₂ (4 bar) pressure, as structurally confirmed by XRD and NMR spectroscopy. By catalysing CO₂ reductive coupling with amines at half the partial pressure of all other main-group catalytic systems with H₂, cationic indium complexes set a new benchmark for such reactions. Therefore, this study not only expands the scope of indium-based catalysis beyond imine hydrogenation but also highlights the potential of ligand-supported indium Lewis acids as catalytic systems for small-molecule activation.

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来源期刊

Journal of Catalysis 工程技术-工程：化工

CiteScore

12.30

自引率

5.50%

发文量

447

审稿时长

31 days

期刊介绍： The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes. The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods. The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.