Introducing Weakly Ligated Tris(trifluoromethyl)copper(III)

ChemistryEurope Pub Date : 2024-03-01 DOI:10.1002/ceur.202400004

Dr. Vladimir Motornov, Martin Procházka, Nora Alpuente, Dr. Pedro Salvador, Prof. Petr Slavíček, Dr. Blanka Klepetářová, Prof. Xavi Ribas, Dr. Petr Beier

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Abstract

Tris(trifluoromethyl)copper(III), Cu(CF₃)₃, was prepared for the first time and fully characterized in the form of weakly coordinated highly reactive solvent neutral adducts (DMF)₂Cu(CF₃)₃ and (MeCN)Cu(CF₃)₃. Free Cu(CF₃)₃ is an elusive molecule of distorted T-shaped geometry with Lewis acid properties, which is stabilized by solvation. Substitution of solvent molecules with monoanionic ligands in mild conditions afforded the first Cu(III)(CF₃)₃ carboxylates [Cu(CF₃)₃(OAc)]⁻ and [Cu(CF₃)₃(OBz)]⁻ and Cu(III) nitrito complex [Cu(CF₃)₃(ONO)]⁻. An improved synthesis of valuable Grushin's trifluoromethylation reagents via the intermediacy of (MeCN)Cu(CF₃)₃ was developed. (DMF)₂Cu(CF₃)₃ demonstrated promising properties in photoinduced radical C-H trifluoromethylation. Oxidation state theoretical studies showed the Cu(CF₃)₃ compounds to be borderline between classical Cu(III) and inverted ligand field Cu(I) assignment.

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引入弱配位三(三氟甲基)铜(III)

首次以弱配位高活性溶剂中性加合物 (DMF)2Cu(CF3)3 和 (MeCN)Cu(CF3)3 的形式制备了三(三氟甲基)铜(III)，即 Cu(CF3)3，并对其进行了全面表征。游离的 Cu(CF3)3 是一种难以捉摸的分子，其几何形状呈扭曲的 T 形，具有路易斯酸特性，并通过溶解而稳定。在温和条件下用单阴离子配体取代溶剂分子，首次得到了 Cu(III)(CF3)3羧酸盐[Cu(CF3)3(OAc)]-和[Cu(CF3)3(OBz)]-以及 Cu(III)亚硝酸盐络合物[Cu(CF3)3(ONO)]-。通过（MeCN）Cu(CF3)3 的中间产物，开发出了一种改进的格鲁欣三氟甲基化试剂的合成方法。(DMF)2Cu(CF3)3在光诱导自由基 C-H 三氟甲基化反应中表现出良好的性能。氧化态理论研究表明，Cu(CF3)3 化合物介于经典的 Cu(III)和反配体场 Cu(I)之间。

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