Kinetics and mechanism of the reactions of ozone with superoxo, hydroperoxo, and hydrido complexes of rhodium(III)
作者:Michael J. Vasbinder、Andreja Bakac
DOI:10.1016/j.ica.2007.11.022
日期:2008.7
Abstract Oxidation of the title complexes with ozone takes place by hydrogen atom, hydride, and electron transfer mechanisms. The reaction with (NH 3 ) 4 (H 2 O)RhH 2+ is a two electron process, believed to involve hydride transfer with a rate constant k = (2.2 ± 0.2) × 10 5 M −1 s −1 and an isotope effect k H / k D = 2. The oxidation of (NH 3 ) 4 (H 2 O)RhOOH 2+ to (NH 3 ) 4 (H 2 O)RhOO 2+ by an apparent
摘要标题化合物与臭氧的氧化是通过氢原子,氢化物和电子转移机理发生的。与(NH 3)4(H 2 O)RhH 2+的反应是两个电子过程,被认为涉及氢化物转移,速率常数k =(2.2±0.2)×10 5 M -1 s -1和一个同位素效应k H / k D =2。通过明显的氢原子转移,(NH 3)4(H 2 O)RhOOH 2+氧化为(NH 3)4(H 2 O)RhOO 2+的过程是定量且快速的, k =(6.9±0.3)×10 3 M -1 s -1,构成了制备超氧配合物的有用途径。后者也被臭氧氧化,但更慢,k = 480±50M -1 s -1。