Oxidation of Benzyl Alcohols with Extraordinarily High Kinetic Isotope Effects

被引：4
作者：
Jo, Myeong Ran [1 ]
Seok, Won K. [1 ]
机构：
[1] Dongguk Univ, Dept Chem, Seoul 100715, South Korea
来源：
BULLETIN OF THE KOREAN CHEMICAL SOCIETY | 2011年 / 32卷 / 08期
关键词：
Ru oxo complex; Mechanisms; High kinetic isotope effects; HYDRIDE TRANSFER; ELECTRON-TRANSFER; PROTON-TRANSFER; COMPLEXES; REACTIVITY; MECHANISM; OXO;
D O I：
10.5012/bkcs.2011.32.8.3003
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Reactions of benzyl alcohol and its derivatives by [Ru-IV(tpy)(dcbpy)(O)](2+) (tpy = 2,2':6',2 ''-terpyridine; dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) leading to the corresponding benzaldehydes in acetonitrile and water have been studied. Kinetic studies show that the reaction is first-order in both alcohol and oxidant, with k = 1.65 (+/- 0.1) M(-1)s(-1) at 20 degrees C, Delta H-double dagger = 4.3 (+/- 0.1) kcal/mol, Delta S-double dagger = -22 (+/- 1) eu, and E-a = 4.9 (+/- 0.1) kcal/mol. High alpha C-H kinetic isotope effects are observed, but O-H solvent isotope effects are negligible. Spectral evidences with the isotope effects suggest that oxidation of benzyl alcohols occurs by a two-electron, hydride transfer. The catalytic cycles of aerobic benzyl alcohol oxidation are employed.
引用
收藏
页码：3003 / 3008
页数：6
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