Theoretical Investigations on the Mechanistic Aspects of O2 Activation by a Biomimetic Dinitrosyl Iron Complex

Ambar Banerjee, Souloke Sen, Ankan Paul*

*Corresponding author for this work

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Though dinitrosyl-iron complexes (DNICs) are largely believed to act as NO carriers, several experiments on model DNICs have suggested that they can also act as nitrating agents in presence of dioxygen. Oxygen activation by DNICs has been implicated as a possible route for protein tyrosine nitration (PTN), which leads to neurodegenerative disorders. Herein using static and dynamic theoretical techniques we unravel a previously unknown dual state mechanistic paradigm for dioxygen activation of a biomimetic nitrating DNIC complex leading to phenolic nitration. Our computations reveal that the model DNIC, the ground electronic state of which is singlet, has a low-lying triplet state and an inherent singlet–triplet spin-crossover of DNICs can be triggered by fluxional changes in the bite angle of the two NO ligands. The presence of a low-lying triplet state in the DNIC affords an avenue for O2 activation other than a direct O2 activation by O2-induced spin-crossover of the singlet ground state. These two low-lying channels facilitate the formation of a peroxynitrite species. Nitration of phenolic substrates is facilitated by the release of NO2. The corresponding minimum energy crossing points (MECP) have been located. Along the reaction path, the changes in the electronic structure scenarios have been studied and interpreted. Our report also sheds light on the plausible mechanistic pathway of PTN by reactive species formed once O2 activation by DNICs have been achieved.

Original languageEnglish
Pages (from-to)3330-3339
Number of pages10
JournalChemistry - A European Journal
Issue number13
Early online date7 Jan 2018
Publication statusPublished - 2 Mar 2018


AB would like to thanks IACS for supporting the research. AP would like to thank DST (WTI project) and BRNS for providing financial support.

FundersFunder number
Department of Science and Technology, Ministry of Science and Technology, India
Board of Research in Nuclear Sciences


    • DNIC
    • iron
    • oxygen activation
    • PTN
    • spin-crossover


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