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Binuclear O-2 activation and hydrogen transfer mechanism for aerobic oxidation of alcohols

机译：双核的0 2激活和氢转移有氧氧化醇的机制

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摘要

A density functional theory study of the aerobic oxidation of 1-phenylethanol into acetophenone catalysed by phenanthroline copper (phenCu) complexes reveals a binuclear O-2 activation and hydrogen transfer mechanism with multiple spin-crossover steps. When di-tert-butyl azodicarboxylate (DBAD) exists, it acts as a stoichiometric oxidant and forms DBADH(2) through successive transfers of the proton and hydride from 1-phenylethanol to DBAD in one transition state with a free energy barrier of 21.8 kcal mol(-1). After the consumption of DBAD, DBADH(2) acts as a co-catalyst assisting O-2 activation and acetophenone formation through binuclear transition states for the cleavages of O-O and C-H bonds with a total free energy barrier of 24.6 kcal mol(-1). Without the presence of DBAD or DBADH(2), the total free energy barrier for the aerobic oxidation of 1-phenylethanol with the participation of two phenCu complexes is 26.1 kcal mol(-1). In all the above three situations, the rate-determining step is the activation of the C-H bond in 1-phenylethanol. The formation of HOO radical and the breaking of the O-O bond in hydrogen peroxide for the formation of a Cu(ii)-hydroxyl dimer are also key steps in the reaction and need the participation of two phenCu complexes.
机译：有氧的密度泛函理论研究1-phenylethanol氧化成苯乙酮铜催化了邻二氮杂菲(phenCu)复合物揭示了一个双核的0 2激活与多个氢转移机制spin-crossover步骤。azodicarboxylate (DBAD)存在,它充当一个化学计量氧化剂和形式DBADH (2)连续的质子和氢化物转移从1-phenylethanol DBAD过渡国家免费21.8千卡的能量势垒摩尔(1)。作为co-catalyst协助0 2激活和苯乙酮形成双核的o - o和分裂的过渡状态碳氢键的总自由能势垒24.6千卡摩尔(1)。或DBADH(2),总免费能量势垒1-phenylethanol的有氧氧化参与两个phenCu复合物是26.1千卡摩尔(1)。速率决定步骤是激活的1-phenylethanol碳氢键。HOO激进的o - o键的断裂过氧化氢的形成铜(ii)羟基二聚体也关键步骤反应,需要两个phenCu的参与复合物。

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