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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 32, Number 8
BKCSDE 32(8)
August 20, 2011 

Oxidation of Benzyl Alcohols with Extraordinarily High Kinetic Isotope Effects
Myeong Ran Jo, Won K. Seok *
Ru oxo complex, Mechanisms, High kinetic isotope effects
Reactions of benzyl alcohol and its derivatives by [RuIV(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−1s−1 at 20 oC, ΔH‡ = 4.3 (± 0.1) kcal/mol, ΔS‡ = −22 (± 1) eu, and Ea = 4.9 (± 0.1) kcal/mol. High α 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.
3003 - 3008
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