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A radical rebound mechanism for the methane oxidation reaction promoted by the dicopper center of a pMMO enzyme: a computational perspective

机译：pMMO酶双铜中心促进甲烷氧化反应的自由基回弹机制：计算角度

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In this article, we investigated the hydroxylation of methane catalyzed by the binuclear copper site of pMMO enzyme, through a radical rebound mechanism. All intermediates and transition states along the reaction coordinate were located and the energies involved in the mechanism calculated using the B3LYP functional including dispersion effects. Our B3LYP-D2 results show that the singlet state of (µ-1,2-peroxo)Cu(II)2 complex plays an important role as the lowest energy species prior to C-H bond activation. A crossing between the singlet and triplet PES is suggested to occur before the cleavage of C-H bond of methane, where the triplet (bis-µ-oxo)Cu(III)2 is very reactive towards activation of the strong C-H bond of methane. The C-H bond activation is the rate-determining step of the reaction, with an activation energy of 18.6 kcal mol-1 relative to the singlet (µ-1,2-peroxo)Cu(II)2 species. Comparison with previous theoretical results for a non-synchronous concerted mechanism suggests the radical rebound mechanism as a possible alternative pathway.
机译：在本文中，我们通过自由基反弹机理研究了pMMO酶的双核铜位催化的甲烷羟基化反应。定位了沿反应坐标的所有中间体和过渡态，并使用B3LYP功能（包括分散效应）计算了该机理所涉及的能量。我们的B3LYP-D2结果表明，（μ-1,2-过氧）Cu（II）2络合物的单重态作为激活C-H键之前的最低能级物质发挥着重要作用。建议在裂解甲烷的C-H键之前发生单重态和三重态PES的交叉，其中三重态（bis-µ-oxo）Cu（III）2对激活甲烷的强C-H键非常有反应性。 C-H键活化是反应的速率确定步骤，相对于单峰（μ-1,2-过氧）Cu（II）2物种，活化能为18.6 kcal mol-1。与以前的非同步协调机制的理论结果进行比较表明，自由基反弹机制是一种可能的替代途径。

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