四价10族金属实现芳烃氟化和三氟甲基化（‘正式’ NiIV、PdIV、PtIV）

IF 23.5 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Coordination Chemistry Reviews Pub Date : 2026-07-15 Epub Date: 2026-03-11 DOI:10.1016/j.ccr.2026.217739

Luca Demonti , Hana Tabikh , Noel Nebra

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引用次数: 0

摘要

有机氟化合物，主要是那些在芳烃中含有F本身或三氟甲基（- CF3）的化合物，在制药/农用化学品工业和材料科学中无处不在，对人类的福祉至关重要。金属介导的芳基- Rf键的形成（Rf = F, CF3）通常受到多种因素的阻碍（F−阴离子的低亲核性，强M−CF3键，难金属化，湿敏感性等）。因此，寻找构建芳基- Rf键的合成方案构成了现代配位/有机金属化学的主要挑战。这篇综述旨在批判性地总结最有吸引力的方法芳基- F/CF3偶联发生在结构表征的MIVRf物种（M = Ni, Pd, Pt; Rf = F, CF3）。本文还介绍并简要讨论了一些“正式”的MIVRf物种经常显示的倒置配体场（ILF）的概念，以及支持ILF电子结构图的光谱和反应性见解。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Arene fluorination and trifluoromethylation enabled by tetravalent group 10 metals ('formally' NiIV, PdIV, PtIV)

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Arene fluorination and trifluoromethylation enabled by tetravalent group 10 metals ('formally' NiIV, PdIV, PtIV)

Organofluorine compounds, mainly those containing F itself or trifluoromethyls (−CF₃) in arenes, are ubiquitous in pharma/agrochemical industries and material science, making them essential to the well-being of mankind. The metal-mediated aryl−R_f bond formations (R_f = F, CF₃) are commonly hampered by multiple factors (low nucleophilicity of the F⁻ anion, strong M−CF₃ bonds, difficult transmetallation, moisture sensitivity, etc.). Accordingly, the finding of synthetic schemes to build aryl−R_f bonds constitutes a major challenge in modern coordination/organometallic chemistry. This review seeks to critically summarize the most appealing approaches to aryl−F/CF₃ couplings taking place from structurally characterized M^IVR_f species (M = Ni, Pd, Pt; R_f = F, CF₃).

The concept of inverted ligand field (ILF) often displayed by some of the ‘formally’ M^IVR_f species compiled herein, together with spectroscopic and reactivity insights supporting the ILF electronic structure picture, is also introduced and briefly discussed.

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来源期刊

Coordination Chemistry Reviews 化学-无机化学与核化学

CiteScore

34.30

自引率

5.30%

发文量

457

审稿时长

54 days

期刊介绍： Coordination Chemistry Reviews offers rapid publication of review articles on current and significant topics in coordination chemistry, encompassing organometallic, supramolecular, theoretical, and bioinorganic chemistry. It also covers catalysis, materials chemistry, and metal-organic frameworks from a coordination chemistry perspective. Reviews summarize recent developments or discuss specific techniques, welcoming contributions from both established and emerging researchers. The journal releases special issues on timely subjects, including those featuring contributions from specific regions or conferences. Occasional full-length book articles are also featured. Additionally, special volumes cover annual reviews of main group chemistry, transition metal group chemistry, and organometallic chemistry. These comprehensive reviews are vital resources for those engaged in coordination chemistry, further establishing Coordination Chemistry Reviews as a hub for insightful surveys in inorganic and physical inorganic chemistry.