Fluorinated ligands and their effects on physical properties and chemical reactivity
Fluorinated ligands and their effects on physical properties and chemical reactivity
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氟化配体及其对物理性质和化学反应性的影响
DOI：
10.1039/d3dt90082g
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发表时间：
2023
影响因子：
4
通讯作者：
Dias, H. V.
中科院分区：
文献类型：
--
作者：
Doerrer, Linda H.;Dias, H. V.
我们很高兴地欢迎道尔顿交易的读者到这个聚光灯收集氟化配体。氟是周期表中电负性最强的元素（鲍林标度为3.98），并且具有非常高的还原电位（2.87 V）。氟的货车范德华半径和共价半径都很短（排在第三位，仅次于第一排元素氢和氦），这使得它的原子序数非常小。虽然F2中的均氟键特别活泼，但一些涉及氟的杂氟键如B-F、Si-F和C-F非常稳定。这些特征对含氟分子的综合影响，特别是那些涉及氟化配体和阴离子的分子，通常是任何其他元素无法比拟的。事实上，氟化支持配体的金属络合物与它们的非氟化烃对应物相比通常显示出相对高的热和氧化稳定性、挥发性以及独特的反应性特征。它们也是氟两相介质和超临界CO2应用的理想选择。含氟阴离子是已知的最弱的供体之一。我们的目的是通过道尔顿交易的领先研究人员的贡献，说明独特的影响氟化配体往往对金属络合物的物理性质和化学反应性。在这个聚光灯下收集的是一系列的论文，展示了令人兴奋的s，p，d和f-区化学，涉及氟目前正在世界各地的实验室。在这个集合中，s区化学集中于较重的第2族元素。氟化芳烃与中性镁和钙络合物相互作用，产生可分离的络合物，如希克斯等人所证明的。（https：//doi. org/10.1039/d1dt01532j）。Sarazin等人描述了具有双（酚盐）和双（氟醇盐）官能化的大环Ca、Sr和Ba络合物以及刘易斯酸度对结构的影响（https：//doi. org/10.1039/d0dt02573a）。
We are pleased to welcome Dalton Transactions readers to this spotlight collection on Fluorinated Ligands. Fluorine is the most electronegative element in the periodic table (3.98 on the Pauling scale) and has a remarkably high reduction potential (2.87 V). The van der Waals and covalent radii of fluorine are quite short (ranked third, only after the first-row elements hydrogen and helium), making it unusually small for its atomic number. Although the homonuclear bond in F2 is particularly reactive, some heteronuclear bonds involving fluorine such as B–F, Si–F, and C–F are remarkably stable. The combined effects of these features on fluorine-containing molecules, especially those involving fluorinated ligands and anions, are often unmatched by any other element. In fact, metal complexes of fluorinated supporting ligands in comparison to their non-fluorinated, hydrocarbon counterparts usually display relatively high thermal and oxidative stability, volatility, as well as unique reactivity profiles. They are also ideal for applications in fluorousbiphase media and supercritical CO2. Fluorine-containing anions are among the weakest donors known. Our aim is to illustrate the unique effects fluorinated ligands often have on physical properties and chemical reactivity of metal complexes through contributions by leading researchers to Dalton Transactions. Assembled in this spotlight collection are a potpourri of papers that show the exciting s, p, d, and f-block chemistry involving fluorine currently underway in laboratories around the world. In this collection, the s-block chemistry focuses on the heavier group 2 elements. Fluorinated arenes interact with neutral Mg and Ca complexes generating isolable complexes as demonstrated by Hicks et al.(https://doi. org/10.1039/d1dt01532j). Sarazin et al. describes macrocyclic Ca, Sr, and Ba complexes with bis (phenolate) and bis (fluoroalkoxide) functionalization and the effects of Lewis acidity on structures (https://doi. org/10.1039/d0dt02573a).