標題: | Mechanistic study for the selective oxidation of benzene and toluene catalyzed by Fe(ClO4)(2) in an H2O2-H2O-CH3CN system |
作者: | Ramu, Ravirala Wanna, Wondemagegn Hailemichael Janmanchi, Damodar Tsai, Yi-Fang Liu, Chih-Cheng Mou, Chung-Yuan Yu, Steve S. -F. 交大名義發表 National Chiao Tung University |
關鍵字: | Iron(II) perchlorate;Oxidation;Hydrogen peroxide;Ring hydroxylation;Chain hydroxylation;Selectivity;Kinetic isotope effect |
公開日期: | 1-十一月-2017 |
摘要: | Iron(II) perchlorate in an H2O-H2O2-CH3CN mixture was used to efficiently carry out C-H bond activations of benzene to form phenol and/or hydroquinone, and of toluene to form benzaldehyde, benzyl alcohol, o-cresol, p-cresol, and/or methyl-p-benzoquinone. The reactions were facilely tuned and controlled to selectively yield either a single or double oxygenation of benzene as well as a sp(3) or sp(2) C-H bond oxidation of toluene. On the basis of HAD kinetic isotope effect data, we determined the aromatic oxidation to mostly proceed by way of formation of an arene oxide or a sigma-complex intermediate from high-valence iron species and to then undergo a 1,2-hydride shift, i.e., NIH-shift rearrangement. (C) 2017 Elsevier B.V. All rights reserved. |
URI: | http://dx.doi.org/10.1016/j.mcat.2017.08.006 http://hdl.handle.net/11536/143925 |
ISSN: | 2468-8231 |
DOI: | 10.1016/j.mcat.2017.08.006 |
期刊: | MOLECULAR CATALYSIS |
Volume: | 441 |
起始頁: | 114 |
結束頁: | 121 |
顯示於類別: | 期刊論文 |