Pérez-Bitrián Alberto, Baya Miguel, Casas José M, Martín Antonio, Menjón Babil, Orduna Jesús
Instituto de Síntesis Química y Catálisis Homogénea (iSQCH), CSIC-Universidad de Zaragoza, C/ Pedro Cerbuna 12, 50009, Zaragoza, Spain.
Instituto de Ciencia de Materiales de Aragón (ICMA), CSIC-Universidad de Zaragoza, C/Pedro Cerbuna 12, 50009, Zaragoza, Spain.
Angew Chem Int Ed Engl. 2018 May 28;57(22):6517-6521. doi: 10.1002/anie.201802379. Epub 2018 Apr 26.
The trans isomer of the organogold(III) difluoride complex [PPh ][(CF ) AuF ] has been obtained in a stereoselective way and in excellent yield by reaction of [PPh ][CF AuCF ] with XeF under mild conditions. The compound is both thermally stable and reactive. Thus, the fluoride ligands are stereospecifically replaced by any heavier halide or by cyanide, the cyanide affording [PPh ][trans-(CF ) Au(CN) ]. The organogold fluoride complexes [CF AuF ] (x=1, 2, 3) have been experimentally detected to arise upon collision-induced dissociation of the [trans-(CF ) AuF ] anion in the gas phase. Their structures have been calculated by DFT methods. In the isomeric forms identified for the open-shell species [CF AuF ] , the spin density residing on the metal center is found to strongly depend on the precise stereochemistry. Based on crystallographic evidence, it is concluded that Au and Ag have similar covalent radii, at least in their most common square-planar geometry.
通过在温和条件下使[PPh₃][CF₃AuCF₃]与XeF₂反应，以立体选择性的方式并以优异的产率获得了有机金（III）二氟化物配合物[PPh₃][(CF₃)₂AuF₂]的反式异构体。该化合物既热稳定又具有反应活性。因此，氟配体可被任何较重的卤化物或氰化物立体选择性地取代，氰化物可得到[PPh₃][反式-(CF₃)₂Au(CN)₂]。已通过实验检测到有机金氟化物配合物[CF₃AuFₓ]（x = 1、2、3）是在气相中[反式-(CF₃)₂AuF₂]阴离子的碰撞诱导解离过程中产生的。它们的结构已通过密度泛函理论（DFT）方法计算得出。在为开壳层物种[CF₃AuFₓ]确定的异构体形式中，发现位于金属中心的自旋密度强烈依赖于精确的立体化学。基于晶体学证据，可以得出结论，金和银具有相似的共价半径，至少在它们最常见的平面正方形几何结构中是如此。
