Winter Marlon, Limberg Niklas, Ellwanger Mathias A, Pérez-Bitrián Alberto, Sonnenberg Karsten, Steinhauer Simon, Riedel Sebastian
Fachbereich Biologie, Chemie, Pharmazie, Institut für Chemie und Biochemie-Anorganische Chemie, Fabeckstr. 34/36, 14195, Berlin, Germany.
On leave from: Instituto de Síntesis Química y Catálisis Homogénea (iSQCH), CSIC-Universidad de Zaragoza, C/ Pedro Cerbuna 12, 50009, Zaragoza, Spain.
Chemistry. 2020 Dec 4;26(68):16089-16097. doi: 10.1002/chem.202002940. Epub 2020 Oct 27.
Trifluoromethylation of [AuF (SIMes)] with the Ruppert-Prakash reagent TMSCF in the presence of CsF yields the product series [Au(CF ) F (SIMes)] (x=1-3). The degree of trifluoromethylation is solvent dependent and the ratio of the species can be controlled by varying the stoichiometry of the reaction, as evidenced from the F NMR spectra of the corresponding reaction mixtures. The molecular structures in the solid state of trans-[Au(CF )F (SIMes)] and [Au(CF ) (SIMes)] are presented, together with a selective route for the synthesis of the latter complex. Correlation of the calculated SIMes affinity with the carbene carbon chemical shift in the C NMR spectrum reveals that trans-[Au(CF )F (SIMes)] and [Au(CF ) (SIMes)] nicely follow the trend in Lewis acidities of related organo gold(III) complexes. Furthermore, a new correlation between the Au-C bond length of the molecular structure in the solid state and the chemical shift of the carbene carbon in the C NMR spectrum is presented.
在氟化铯存在下,用鲁珀特 - 普拉卡什试剂三甲基硅基三氟甲基(TMSCF₃)对[AuF(SIMes)]进行三氟甲基化反应,得到产物系列[Au(CF₃)ₓF(SIMes)](x = 1 - 3)。三氟甲基化程度取决于溶剂,并且通过改变反应的化学计量比可以控制这些物种的比例,这从相应反应混合物的¹⁹F NMR光谱中得到证实。给出了反式 - [Au(CF₃)F(SIMes)]和[Au(CF₃)₂(SIMes)]固态下的分子结构,以及合成后一种配合物的选择性路线。计算得到的SIMes亲和力与¹³C NMR光谱中卡宾碳化学位移的相关性表明,反式 - [Au(CF₃)F(SIMes)]和[Au(CF₃)₂(SIMes)]很好地遵循了相关有机金(III)配合物的路易斯酸度趋势。此外,还给出了固态分子结构中Au - C键长与¹³C NMR光谱中卡宾碳化学位移之间的新相关性。