一价金α-三氟甲基卡宾：合成、表征及反应活性研究
Gold(I) α-Trifluoromethyl Carbenes: Synthesis, Characterization and Reactivity Studies.
作者信息
Rigoulet Mathilde, Vesseur David, Miqueu Karinne, Bourissou Didier
机构信息
CNRS/Université Paul Sabatier, Laboratoire Hétérochimie, Fondamentale et Appliquée (LHFA, UMR 5069), 118 Route de Narbonne, 31062, Toulouse Cedex 09, France.
CNRS/Université de Pau et des Pays de l'Adour, E2S-UPPA, Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux (IPREM, UMR 5254), Hélioparc, 2 Avenue du Président Angot, 64053, Pau Cedex 09, France.
出版信息
Angew Chem Int Ed Engl. 2022 Jun 20;61(25):e202204781. doi: 10.1002/anie.202204781. Epub 2022 May 3.
Aryl trifluoromethyl diazomethanes 2-R (R=Ph, OMe, CF ) are readily decomposed by the (o-carboranyl)diphosphine gold(I) complex 1. The resulting α-CF substituted carbene complexes 3-R have been characterized by multi-nuclear NMR spectroscopy as well as X-ray crystallography (for 3-Ph). The bonding situation was thoroughly assessed by computational means, showing stabilization of the electrophilic carbene center by π-donation from the aryl substituent and backdonation from Au, as enhanced by the chelating P^P ligand. Reactivity studies under stoichiometric and catalytic conditions substantiate typical carbene-type behavior for 3-Ph.
芳基三氟甲基重氮甲烷2-R（R = Ph、OMe、CF）很容易被（邻碳硼烷基）二膦金（I）配合物1分解。生成的α-CF取代卡宾配合物3-R已通过多核核磁共振光谱以及X射线晶体学（对于3-Ph）进行了表征。通过计算方法全面评估了键合情况，结果表明，通过芳基取代基的π-给予和金的反馈给予，亲电卡宾中心得到了稳定，而螯合的P^P配体进一步增强了这种稳定作用。在化学计量和催化条件下的反应性研究证实了3-Ph具有典型的卡宾型行为。
Zotero 插件