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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Isolation of OH-bridged Ag(i)/Cu(iii) and ion-pair Cu(i)/Cu(iii) trifluoromethyl complexes with monophosphines
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Isolation of OH-bridged Ag(i)/Cu(iii) and ion-pair Cu(i)/Cu(iii) trifluoromethyl complexes with monophosphines

机译：用单膦分离OH-桥合的Ag（I）/ Cu（III）和离子对Cu（I）/ Cu（III）三氟甲基复合物

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摘要

Cu(III)-CF3 complexes are important intermediates of both synthetic and mechanistic interest. This study describes the isolation, and spectroscopic and X-ray crystallographic characterization of Cu-III-CF3 complexes 2-4 with typical monophosphine ligands PPh3 and Buchwald-type biarylmonophosphines. Distinct from the ion-pair [P2Cu(I)](+)[Cu(III)(CF3)(4)](-) structures of 2 and 4 (P: PPh3 or SPhos), complex 3 exhibits a novel OH-bridged Ag(I)-Cu(III) dinuclear structure with XPhos-coordinated linear Ag(I) and square planar Cu(III) components. This is the first heterobimetallic Cu(III)-CF3 complex confirmed by both solution-phase NMR spectroscopy and solid state X-ray crystal structure analysis. Complex 3 is found to have the LUMO orbital of major sigma*(Cu-CF3) nature and electrophilic CF3 ligands. Accordingly, complex 3 is able to trifluoromethylate 2 equivalents of aryl boronic acids in up to quantitative yields, regardless of the inert or oxidative conditions. In contrast, the ion-pair complexes 2 and 4 show low reactivity. This study enriches the coordination and reactivity chemistry of Cu(III)-CF3 compounds and shows the feasibility of modulation of structures and reactivity by ligand design, which may inspire future efforts on Cu(III)-CF3 chemistry.
机译：Cu（III）-CF3复合物是合成和机械利益的重要中间体。本研究描述了Cu-III-CF3配合物2-4的分离，光谱和X射线结晶表征，具有典型的单膦配体PPH3和Buchwald型丙芳烃。不同于离子对的[P2CU（I）]（+）[Cu（III）（CF 3）（4）]（ - ）结构为2和4（P：PPH3或SPHO），复杂3展示了一种新颖的OH-桥接AG（I）-Cu（III）二核结构，具有Xphos-Coordinated Linear Ag（I）和方形平面Cu（III）组分。这是通过溶液相NMR光谱和固态X射线晶体结构分析证实的第一杂二种金属Cu（III）-CF 3复合物。发现复合物3具有主要的Sigma *（Cu-CF3）性质和亲电CF3配体的Lumo轨道。因此，络合物3能够在不管惰性或氧化条件的情况下进行三氟甲基化芳基硼酸的2当量芳基硼酸。相反，离子对复合物2和4显示低反应性。该研究丰富了Cu（III）-CF3化合物的配位和反应性化学，并显示了通过配体设计调节结构和反应性的可行性，这可能激发Cu（III）-CF3化学的未来努力。

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