Oxo-bridged diiron(III) complexes [Fe 2 O(L 1 ) 2 (H 2 O) 2 ](ClO 4 ) 4 ( 1 ) and [Fe 2 O(L 2 ) 2 (H 2 O) 2 ](ClO 4 ) 4 ( 2 ), where L 1 and L 2 are tetradentate N -donor N , N ′-bis(2-pyridylmethyl)-1,2-cyclohexanediamine and N , N ′-bis(2-pyridylmethyl)ethane-1,2-diamine respectively, have been isolated as synthetic models of non-heme iron oxygenases and characterized by physicochemical and spectroscopic methods. Both the complexes have been studied as catalysts for the oxyfunctionalization of saturated hydrocarbons using green hydrogen peroxide (H 2 O 2 ) as oxidant under mild conditions. The selectivity (A/K) and regioselectivity (3°/2°) in oxidative C–H functionalization of alkanes suggests the involvement of metal-based intermediate in the oxygenation reaction. The catalytic efficiency is found to be strongly dependent on the presence of acetic acid. Remarkable increase in conversion and selectivity favoring the formation of alcohols in the oxidation of cyclohexane and cyclooctane and exclusive hydroxylation of adamantane with drastic enhancement of regioselectivity has been achieved by the addition of acetic acid in the presence of H 2 O 2 .

中文翻译：

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非血红素氧桥二铁 (III) 配合物催化氧化饱和烃：乙酸在氧化反应中的作用

氧桥连二铁(III)配合物[Fe 2 O(L 1 ) 2 (H 2 O) 2 ](ClO 4 ) 4 ( 1 )和[Fe 2 O(L 2 ) 2 (H 2 O) 2 ]( ClO 4 ) 4 ( 2 )，其中L 1 和L 2 是四齿N-供体N , N '-双(2-吡啶甲基)-1,2-环己二胺和N , N '-双(2-吡啶甲基)乙烷- 1,2-二胺分别作为非血红素铁加氧酶的合成模型被分离出来，并通过物理化学和光谱方法表征。两种配合物均已被研究作为在温和条件下使用绿色过氧化氢 (H 2 O 2 ) 作为氧化剂对饱和烃进行氧官能化的催化剂。烷烃氧化 C-H 官能化的选择性 (A/K) 和区域选择性 (3°/2°) 表明金属基中间体参与了氧化反应。发现催化效率强烈依赖于乙酸的存在。通过在 H 2 O 2 存在下加入乙酸，在环己烷和环辛烷的氧化过程中，转化率和选择性显着增加，有利于醇的形成，金刚烷的独家羟基化也显着提高了区域选择性。