Shimizu Ikuma, Morimoto Yuma, Velmurugan Gunasekaran, Gupta Tulika, Paria Sayantan, Ohta Takehiro, Sugimoto Hideki, Ogura Takashi, Comba Peter, Itoh Shinobu
Department of Material and Life Science, Division of, Advanced Science and Biotechnology, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka, 565-0871, Japan.
Universität Heidelberg, Anorganisch-Chemisches Institut and Interdisciplinary Center for Scientific Computing, INF 270, 69120, Heidelberg, Germany.
Chemistry. 2019 Aug 22;25(47):11157-11165. doi: 10.1002/chem.201902669. Epub 2019 Aug 1.
A tetrahedral Cu alkylperoxido complex [Cu (TMG tach)(OOCm)] (1 ) (TMG tach={2,2',2''-[(1s,3s,5s)-cyclohexane-1,3,5-triyl]tris-(1,1,3,3-tetramethyl guanidine)}, OOCm=cumyl peroxide) is prepared and characterized by UV/Vis, cold-spray ionization mass spectroscopy (CSI-MS), resonance Raman, and EPR spectroscopic methods. Product analysis of the self-decomposition reaction of 1 in acetonitrile (MeCN) indicates that the reaction involves O-O bond homolytic cleavage of the peroxide moiety with concomitant C-H bond activation of the solvent molecule. When an external substrate such as 1,4-cyclohexadiene (CHD) is added, the O-O bond homolysis leads to C-H activation of the substrate. Furthermore, the reaction of 1 with 2,6-di-tert-butylphenol derivatives produces the corresponding phenoxyl radical species (ArO ) together with a Cu complex through a concerted proton-electron transfer (CPET) mechanism. Details of the reaction mechanisms are explored by DFT calculations.
制备了一种四面体铜烷基过氧络合物[Cu (TMG tach)(OOCm)] (1)（TMG tach = {2,2',2''-[(1s,3s,5s)-环己烷-1,3,5-三基]三-(1,1,3,3-四甲基胍)}，OOCm = 过氧化异丙苯），并通过紫外/可见光谱、冷喷雾电离质谱(CSI-MS)、共振拉曼光谱和电子顺磁共振光谱方法对其进行了表征。对1在乙腈(MeCN)中的自分解反应进行产物分析表明，该反应涉及过氧化物部分的O-O键均裂，同时伴随着溶剂分子的C-H键活化。当加入外部底物如1,4-环己二烯(CHD)时，O-O键均裂导致底物的C-H活化。此外，1与2,6-二叔丁基苯酚衍生物的反应通过协同质子-电子转移(CPET)机制产生相应的苯氧基自由基物种(ArO)和一种铜络合物。通过密度泛函理论(DFT)计算探索了反应机理的细节。
