聚钽钨酸盐稳定铁催化剂对苯基C-H键羰基化反应的影响。

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-09-07 DOI:10.1021/acs.inorgchem.5c02238

Hanhan Chen, , , Xinyi Ma, , , Haojie Xu, , , Pengtao Ma, , , Jingping Wang*, , and , Jingyang Niu*,

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引用次数: 0

摘要

苯基C(sp3)-H键选择性氧化成酮对于精细化学品的生产至关重要，但通常需要在恶劣条件下使用有毒/贵金属催化剂。虽然铁基配合物最近被用作光催化C-H键活化的催化剂，但大多数系统都是通过均相催化进行的。在可见光下以O2作为氧化剂开发光驱动策略是非常重要的。本文以K11Li[P2W12(TaO2)6O56]·19H2O （{P2W12(TaO2)6}）、[fe30o (CH3COO)6(H2O)3]NO3·4H2O和[fe30o (O2CH)6(H2O)3]NO3为原料，合成了[Fe4(CH3COO)2(OH)5(H2O)9]2[Fe4(CH3COO)(OH)4(H2O)10（P2W12 Ta6O62)]2·166H2O(1)）、K4[Fe4(HCOO)2(OH) 2(H2O)14（P2W12Ta6O62)]2·121H2O(3)）和K4H2[Fe4(HCOO)2(H2O)12(P2W12Ta6O62)]2·121H2O(3)。{P2W12(TaO2)6}中ta结合的氧原子的碱性/亲核性增强，消除了过氧基团，使金属离子结合。催化剂1通过前所未有的fe配体- pom合作实现了定量THN氧化（99%），表现出广泛的可见吸收，定制的能带位置和长时间的电荷分离。作为第一个在O2气氛下进行好氧光氧化THN的多相系统，它为多金属氧酸盐光催化剂的设计设定了新的标准。然而，蓝光照射的要求和有限的衬底范围突出了未来优化的领域。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Polytantalotungstates Stabilized Iron Catalysts for Carbonylation of Benzylic C–H Bonds

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Polytantalotungstates Stabilized Iron Catalysts for Carbonylation of Benzylic C–H Bonds

Selective oxidation of benzylic C(sp³)–H bonds to ketones is critical to the production of fine chemicals but typically requires toxic/precious metal catalysts under harsh conditions. While iron-based complexes have recently served as catalysts for photocatalytic C–H bond activation, most systems operate via homogeneous catalysis. Developing a light-driven strategy under visible light with O₂ as an oxidant is of major importance. Here, we have synthesized three Fe-based polytantalotungstates, [Fe₄(CH₃COO)₂(OH)₅(H₂O)₉]₂[Fe₄(CH₃COO)(OH)₄(H₂O)₁₀(P₂W₁₂ Ta₆O₆₂)]₂·166H₂O (1), K₄[Fe₄(OH)₂(H₂O)₁₄(P₂W₁₂Ta₆O₆₂)]₂·72H₂O (2), and K₄H₂[Fe₄(HCOO)₂(OH)(H₂O)₁₂(P₂W₁₂Ta₆O₆₂)]₂·121H₂O (3), using K₁₁Li[P₂W₁₂(TaO₂)₆O₅₆]·19H₂O ({P₂W₁₂(TaO₂)₆}), [Fe₃O(CH₃COO)₆(H₂O)₃]NO₃·4H₂O, and [Fe₃O(O₂CH)₆(H₂O)₃]NO₃. Enhanced basicity/nucleophilicity of Ta-bound oxygen atoms in {P₂W₁₂(TaO₂)₆} eliminates peroxo groups, enabling metal-ion incorporation. Catalyst 1 achieves quantitative THN oxidation (99%) through unprecedented Fe-ligand-POM cooperation, exhibiting broad visible absorption, tailored band positions, and prolonged charge separation. As the first robust heterogeneous system for aerobic THN photooxidation under an O₂ atmosphere, it sets new standards for polyoxometalate photocatalyst design. However, the requirement of blue-light irradiation and limited substrate scope highlight areas for future optimization.

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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.