Aryl-BIAN-ligated silver(i) trifluoromethoxide complex. Issue 45 (6th July 2015)

• Record Type: Journal Article
• Authors: Chen, Shouxiong; Huang, Yangjie; Fang, Xin; Li, Haohong; Zhang, Zhongxing; Hor, T. S. Andy; Weng, Zhiqiang
• Is Part Of: Dalton transactions. Volume 44:Issue 45(2015)
• Page Start: 19682
• Page End: 19686
• Publication Date: 2015-07-06
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5dt02078f
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The complex (Aryl-BIAN)AgOCF3 has been synthesised and structurally characterised. The reactivity towards trifluoromethoxylation of benzyl bromides has also been examined. Abstract : 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 of1 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 of1 and the bonding characters of the OCF3 group. The reactivity of1 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.