Construction of Heterovalent Cu(I)/Cu(II) Dual-Site Catalysts via Terpyridine Ligands: Topological Modulation and Synergistic Catalysis.

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-09-22 DOI:10.1021/acs.inorgchem.5c03424

Yi Han,Xuefei Bai,Ning Wang,Qiangqiang Dong,Die Liu,Pingshan Wang,Yiming Li

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Abstract

Dual-site heterogeneous catalysts hold great promise for the efficient conversion of substances. However, challenges remain in the precise construction of dual-site heterovalent structures and the realization of efficient cocatalysis. This study reports the construction of dinuclear heterovalent metal catalysts via pyridine-based ligands and cuprous iodide clusters, and the investigation of their catalytic activities in the oxidative coupling of benzylamine. By adjusting the ligand geometry, structural tuning from one-dimensional (1D) chains to two-dimensional (2D) cyclic frameworks was achieved to obtain a series of dinuclear heterovalent metal catalysts (DCu-T1 to DCu-T6). Among them, the cyclic DCu-T6 exhibited superior catalytic performance in benzylamine coupling, with a conversion rate of 99%, which significantly surpassed that of the mononuclear control catalyst TPY-Cu (20%). Mechanism studies reveal a synergistic effect between binuclear metal sites of different valence states, which is validated by electron paramagnetic resonance (EPR), in situ infrared (IR) spectroscopy, and theoretical calculations. These results provide a strategy for the construction of high-performance dual-site heterovalent catalysts and clarify the atomic-level catalytic mechanism responsible for their enhanced efficiency.

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三吡啶配体构建Cu(I)/Cu（II）二元催化剂：拓扑调制和协同催化。

双位点非均相催化剂对物质的高效转化具有很大的前景。然而，在精确构建双位点杂价结构和实现高效共催化方面仍存在挑战。本研究报道了以吡啶配体和碘化亚铜簇为载体构建双核杂价金属催化剂，并研究了它们在苯胺氧化偶联中的催化活性。通过调整配体的几何形状，实现了从一维（1D）链到二维（2D）循环框架的结构调整，得到了一系列双核异价金属催化剂（DCu-T1至DCu-T6）。其中，环型DCu-T6在苯胺偶联反应中表现出优异的催化性能，转化率达99%，明显超过单核控制催化剂TPY-Cu（20%）。机制研究揭示了不同价态双核金属位之间的协同效应，并通过电子顺磁共振（EPR）、原位红外（IR）光谱和理论计算验证了这一理论。这些结果为构建高性能的双位点杂价催化剂提供了策略，并阐明了其提高效率的原子级催化机理。

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

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.