Yi Chae S, Kwon Ki-Hyeok, Lee Do W
Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201-1881, USA.
Org Lett. 2009 Apr 2;11(7):1567-9. doi: 10.1021/ol900097y.
The cationic complex (pymox-Me(2))RuCl(2)BF(4)(-) was found to be a highly effective catalyst for the C-H bond oxidation reaction of arylalkanes in water. For example, the treatment of ethylbenzene (1.0 mmol) with t-BuOOH (3.0 mmol) and 1.0 mol % of the Ru catalyst in water (3 mL) cleanly produced PhCOCH(3) at room temperature. Both a large kinetic isotope effect (k(H)/k(D) = 14) and a relatively large Hammett value (rho = -1.1) suggest a solvent-caged oxygen rebounding mechanism via a Ru(IV)-oxo intermediate species.
发现阳离子配合物(pymox-Me(2))RuCl(2)BF(4)(-)是水中芳基烷烃C-H键氧化反应的高效催化剂。例如，在室温下，将乙苯（1.0 mmol）与叔丁基过氧化氢（3.0 mmol）和1.0 mol%的钌催化剂在水（3 mL）中反应，可顺利生成苯乙酮（PhCOCH(3)）。较大的动力学同位素效应（k(H)/k(D)=14）和相对较大的哈米特值（rho = -1.1）表明，反应通过Ru(IV)-氧代中间体物种经由溶剂笼氧反弹机制进行。
