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

页码：3003 / 3008

页数：6

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