Unusual reaction of a tungsten alkylidyne complex with ***,characterization,and crystal structures of oxo trimers

作     者：DOUGAN Brenda A. 

作者机构：Department of ChemistryUniversity of Tennessee 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2011年第54卷第12期

页      面：1903-1908页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：supported by the US National Science Foundation(CHE-0749651 & CHE-1012173) 

主　　题：反应动力学 羰基络合物 三烷基 三聚体 重水 晶体结构 表征 同位素效应 

摘      要：The reaction of the alkyl alkylidyne W(CH2CMe3)3(CSiMe3)(1) with H2O in THF and with D2O in benzene-d6 gave two new trimeric oxo complexes:W3O3(μ=O)3(CH2CMe3)6(THF)3(2) and [W3O3(μ=O)3(CH2CMe3)6(D2O)3]·2benzene-d6(3·2benzene-d6),respectively,each containing two alkyl ligands per W *** is in contrast to the dimer W2O2(μ-O)(CH2CMe3)6,containing three alkyl ligands per W atom,from the previously reported reaction of the alkyl alkylidyne analog W(CH2CMe3)3-(≡CCMe3) with *** the reaction of 1 with D2O in THF,an unstable intermediate W2O2(μ-O)(CD2SiMe3)2(CH2CMe3)4(4-d4) was *** studies of the reactions of 1 with excess H2O and D2O in THF-d8,yielding 4 and 4-d4,respectively,give a kinetic isotope effect(KIE) of 3.46(3) at 298(1) K,suggesting that the disappearance of 1 is a rate-determining step.