Kinetics and Mechanism of the Oxidation of Alkylaromatic Compounds by a trans-Dioxoruthenium(VI) Complex

• Published in: Inorganic chemistry Vol. 42; no. 24; pp. 8011 - 8018
• Main Authors: Lam, William W. Y, Yiu, Shek-Man, Yiu, Douglas T. Y, Lau, Tai-Chu, Yip, Wing-Ping, Che, Chi-Ming
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 01.12.2003
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic034782j

The oxidations of a series of 21 alkylaromatic compounds by trans-[RuVI(L)(O)2]2+ (L = 1,12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8-dioxacyclopentadecane) have been studied in CH3CN. Toluene is oxidized to benzaldehyde and a small amount of benzyl alcohol. 9,10-Dihydroanthracene is oxidized to anthracene and anthraquinone. Other substrates give oxygenated products. The kinetics of the reactions were monitored by UV−vis spectrophotometry, and the rate law is:  −d[RuVI]/dt = k 2[RuVI][ArCH3]. The kinetic isotope effects for the oxidation of toluene/d 8−toluene and fluorene/d 10−fluorene are 15 and 10.5, respectively. A plot of ΔH ⧧ versus ΔS ⧧ is linear, suggesting a common mechanism for all the substrates. In the oxidation of para-substituted toluenes, a linear correlation between log k 2 and σ0 values is observed, consistent with a benzyl radical intermediate. A linear correlation between ΔG ⧧ and ΔH 0 (the difference between the strength of the bond being broken and that being formed in a H-atom transfer step) is also found, which strongly supports a hydrogen atom transfer mechanism for the oxidation of these substrates by trans-[RuVI(L)(O)2]2+. The slope of (0.61 ± 0.06) is in reasonable agreement with the theoretical slope of 0.5 predicted by Marcus theory.