Electronic Structure of N-Bridged High-Valent Diiron-Oxo.,Chemistry - A European Journal

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Electronic Structure of N-Bridged High-Valent Diiron-Oxo.
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2019-09-05 , DOI: 10.1002/chem.201902766
Quan Manh Phung _{1,

2} , Kristine Pierloot ₁

Affiliation

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 FeV -FeIV 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.

中文翻译：

N桥高价Diiron-Oxo的电子结构。

密度泛函理论（DFT）和基于密度矩阵重整化组（DMRG-CASPT2）的先进的从头算技术被用来研究参与H-抽象反应的反应性N桥联高价二价铁-氧代物种。我们详细研究了两个重要的双重态，具有两个铁（IV）中心的基态和混合价FeV -FeIV激发态。我们发现后者处于低洼状态。此外，它的电子结构和自旋密度暗示它具有比基态高得多的H吸收反应性。这种低洼的激发态可能是该二铁氧代物种对甲烷具有高氧化反应性的原因。

更新日期：2019-09-05

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