Chen Shouxiong, Huang Yangjie, Fang Xin, Li Haohong, Zhang Zhongxing, Hor T S Andy, Weng Zhiqiang
State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, 350108, China.
Dalton Trans. 2015 Dec 7;44(45):19682-6. doi: 10.1039/c5dt02078f. Epub 2015 Jul 6.
A reaction of acetonitrile-solvated AgOCF3 with 1 equiv. of Aryl-BIAN ligand in THF at room-temperature afforded the silver(i) complex (Aryl-BIAN)AgOCF3 (1) in 75% yield. The crystal structure of this silver(i) trifluoromethoxide was determined by single-crystal X-ray crystallography. The molecular structure of 1 shows the metal centre bound to one molecule of BIAN, one trifluoromethoxide and one THF solvate, resulting in a distorted tetrahedral silver. Density functional theory (DFT) calculations and the natural bond orbital (NBO) analysis were conducted to give insights into the electronic structure of 1 and the bonding characters of the OCF3 group. The reactivity of 1 towards trifluoromethoxylation of organic halides was also examined; a reaction with benzyl bromides gave the desired products of benzyl trifluoromethyl ethers in good to excellent yields.
在室温下，乙腈溶剂化的AgOCF₃与1当量的芳基 - BIAN配体在四氢呋喃（THF）中反应，以75%的产率得到银（Ⅰ）配合物（芳基 - BIAN）AgOCF₃（1）。通过单晶X射线晶体学确定了该三氟甲氧基银（Ⅰ）的晶体结构。1的分子结构表明金属中心与一个BIAN分子、一个三氟甲氧基和一个THF溶剂化物相连，形成一个扭曲的四面体银。进行了密度泛函理论（DFT）计算和自然键轨道（NBO）分析，以深入了解1的电子结构和OCF₃基团的键合特征。还研究了1对有机卤化物三氟甲氧基化的反应活性；与苄基溴的反应以良好至优异的产率得到了所需的苄基三氟甲基醚产物。
