Reactivity of [WCl6] with Ethers: A Joint Computational, Spectroscopic and Crystallographic Study

详细信息    查看全文

• 作者：Marco Bortoluzzi ; Fabio Marchetti ; Guido Pampaloni and Stefano Zacchini
• 刊名：European Journal of Inorganic Chemistry
• 出版年：2016
• 出版时间：July 2016
• 年：2016
• 卷：2016
• 期：19
• 页码：3169-3177
• 全文大小：1606K
• ISSN：1099-0682c

文摘

The reactions of [WCl₆] with a series of ethers have been performed in chlorinated solvent and elucidated by means of analytical, spectroscopic and DFT methods. The addition of tetrahydropyran (thp) or 1,4-dioxane to [WCl₆] resulted in the reversible formation of the adducts WCl₆···L [L = thp (1a), 1,4-dioxane (1b)], detected in solution by NMR spectroscopy. The reaction of [WCl₆] with thp in a molar ratio of 1:2 in chloroform at reflux afforded [WOCl₄(thp)] (2a), which was isolated in 51 % yield. [WOCl₄(OMe₂)] (2b) and [WOCl₃(OMe₂)₂] (3a) were isolated in yields of 53 and 18 %, respectively, from the reaction of [WCl₆] with an excess of dimethyl ether. [WOCl₃(OEt₂)₂] (3b) was the only identified metal compound produced from the reaction of [WCl₆] and OEt₂ (1:2 molar ratio). According to NMR studies, the oxide ligand in 2a,b and 3a,b was generated by double C–O bond cleavage involving one equivalent of organic reactant. The 1:1 reaction of [WCl₆] with 1,2-diethoxyethane led to [WCl₅(κ¹-OCH₂CH₂OEt)] (4) and a minor amount of [WCl₄(κ²-EtOCH₂CH₂OEt)] (5). The aryl oxide compound [WCl₅(OPh)] (6) was prepared in 62 % yield from the reaction of [WCl₆] and anisole by selective C_sp3–O bond activation. The prolonged heating of a mixture of [WCl₆] and diphenyl ether in 1,2-dichloroethane led to the isolation of the W^V complex [WCl₅(OPh₂)] (7). The molecular structures of 2a and 3a were ascertained by X-ray diffraction.