Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Oxidation of Benzyl Alcohols with Extraordinarily High Kinetic Isotope Effects

  • Received : 2011.03.11
  • Accepted : 2011.04.21
  • Published : 2011.08.20
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Abstract

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 (${\pm}$ 0.1) $M^{-1}s^{-1}$ at $20^{\circ}C$, ${\Delta}H^{\ddag}$ = 4.3 (${\pm}$ 0.1) kcal/mol, ${\Delta}S^{\ddag}$ = -22 (${\pm}$ 1) eu, and $E_a$ = 4.9 (${\pm}$ 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.

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