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Electronic Structure of N ‐Bridged High‐Valent Diiron‐Oxo
Author(s) -
Phung Quan Manh,
Pierloot Kristine
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201902766
Subject(s) - density matrix renormalization group , excited state , density functional theory , reactivity (psychology) , valence (chemistry) , chemistry , ab initio , ground state , electronic structure , computational chemistry , crystallography , atomic physics , renormalization group , physics , quantum mechanics , organic chemistry , medicine , alternative medicine , pathology
Abstract 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 V ‐Fe IV 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.