Clear elucidation of the oxidative relationships of the active metal hydroperoxide moiety with its corresponding metal oxo and hydroxo intermediates would help the understanding of the different roles they may play in redox metalloenzymes and oxidation chemistry. Using an Mn(Me(2)EBC)Cl(2) complex, it was found that, in t-butanol-water (4 : 1) with excess H(2)O(2) at pH 1.5, the Mn(IV)-OOH moiety may exist in the catalytic solution with a mass signal of m/z = 358.1, which provides a particular chance to investigate its oxidative properties. In catalytic oxidations, the Mn(IV)-OOH moiety demonstrates a relatively poor activity in hydrogen abstraction from diphenyl methane and ethylbenzene with TOF of only 1.2 h(-1) and 1.1 h(-1) at 50 °C, whereas it can efficiently oxygenate diphenyl sulfide, methyl phenyl sulfide and benzyl phenyl sulfide with TOF of 13.8 h(-1), 15.4 h(-1) and 17.8 h(-1), respectively. In mechanistic studies using H(2)(18)O and H(2)(18)O(2), it was found that, in the Mn(IV)-OOH moiety mediated hydrogen abstraction and sulfide oxygenations, the reaction proceeds by two parallel pathways: one by direct oxygen insertion/transfer, and the other by plausible electron transfer. Together with a good understanding of the corresponding manganese(IV) oxo and hydroxo intermediates, this work provides the first chance to compare the reactivity differences and similarities of the active metal oxo, hydroxo and hydroperoxide intermediates. The available evidence reveals that the Mn(IV)-OOH moiety has a much more powerful oxidizing capability than the corresponding Mn(IV)=O and Mn(IV)-OH functional groups in both hydrogen abstraction and oxygenation.
The Mn+OH moiety in a manganese(IV) complex has more powerful electron‐transfer capability than its corresponding Mn+O moiety. An Mn+O moiety can abstract hydrogen from a substrate, then rebind the OH group from its reduced M(n−1)+OH form to the substrate radical. In contrast, the active center with an Mn+OH cannot perform similar rebound from its reduced M(n−1)+OH2 group (see scheme; HAT=hydrogen abstraction).
Clarifying how versatile physicochemical parameters of an active metal intermediate affect its reactivity would help to understand its roles in chemical and enzymatic oxidations. The influence of the net charge on electron transfer and hydrogen abstraction reactions of a manganese(IV) species having hydroxide ligand has been investigated here. It was found that increasing one unit of the positive net charge from 2+ to 3+ would accelerate its electron-transfer rate by 10−20 fold in oxygenation of tris(4-methoxyphenyl)phosphine. In contrast, the hydrogen abstraction rate is insensitive to its net charge change, and the insensitivity has been attributed to the compensation effect between the redox potential and pK a , which determine the hydrogen abstraction capability of a metal ion. Similar net-charge-promoted electron transfer but not hydrogen abstraction has also been observed in intramolecular electron transfer and hydrogen abstraction reactions when using thioxanthene as substrate. Together with the previous understanding of the reactivity of the identical manganese(IV) species having Mn IV −OH or Mn IV =O functional groups, the relationships of the oxidative reactivity of an active metal intermediate with its physicochemical parameters such as the net charge, the redox potential and the metal−oxygen bond order (M−O versus MO) have been discussed with this manganese(IV) model.
The kinetics of hydrogen abstraction by manganese(IV) species having hydroxo or oxo group reveals that they have very similar reactive characters in the transition state of hydrogen abstraction.
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