%0 Journal Article %A W. Y. Lam, William %A Yiu, Shek-Man %A Yiu, Douglas T. Y. %A Lau, Tai-Chu %A Yip, Wing-Ping %A Che, Chi-Ming %D 2003 %T Kinetics and Mechanism of the Oxidation of Alkylaromatic Compounds by a trans-Dioxoruthenium(VI) Complex %U https://acs.figshare.com/articles/journal_contribution/Kinetics_and_Mechanism_of_the_Oxidation_of_Alkylaromatic_Compounds_by_a_i_trans_i_Dioxoruthenium_VI_Complex/3358072 %R 10.1021/ic034782j.s001 %2 https://acs.figshare.com/ndownloader/files/5197381 %K Ru %K Other substrates %K toluene %K k 2 %K 21 alkylaromatic compounds %K Alkylaromatic Compounds %K oxidation %K Δ H 0 %K UV %K Marcus theory %K fluorene %K CH 3 CN %K log k 2 %K benzyl alcohol %K σ 0 values %K rate law %K isotope effects %K VI %K hydrogen atom transfer mechanism %K oxygenated products %K correlation %X 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 = k2[RuVI][ArCH3]. The kinetic isotope effects for the oxidation of toluene/d8−toluene and fluorene/d10−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 k2 and σ0 values is observed, consistent with a benzyl radical intermediate. A linear correlation between ΔG and ΔH0 (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. %I ACS Publications