Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Leuven, 3001, Belgium.
Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya, 464-8602, Japan.
Chemistry. 2019 Sep 25;25(54):12491-12496. doi: 10.1002/chem.201902766. Epub 2019 Sep 5.
Density functional theory (DFT) and an advanced ab initio technique based on density matrix renormalization group (DMRG-CASPT2) were employed to investigate a reactive N-bridged high-valent diiron-oxo species involved in H-abstraction reactions. We studied in detail two important doublet states, the ground state with two iron(IV) centers and a mixed valence Fe -Fe excited state. We found that the latter state is low-lying. Furthermore, its electronic structure and spin density imply that it has significantly higher H-abstraction reactivity than the ground state. This low-lying excited state might be the reason behind the high oxidation reactivity of this diiron-oxo species towards methane.
密度泛函理论（DFT）和基于密度矩阵重整化群（DMRG-CASPT2）的高级从头算技术被用于研究涉及 H 提取反应的反应性 N 桥联高价双铁-氧物种。我们详细研究了两种重要的双重态，具有两个铁（IV）中心的基态和混合价 Fe-Fe 激发态。我们发现后一种状态是低能的。此外，其电子结构和自旋密度表明它比基态具有更高的 H 提取反应性。这种低能激发态可能是这种双铁-氧物种对甲烷具有高氧化反应性的原因。
