Computational Mechanistic Insights on the NO Oxidation Reaction Catalyzed by Non-Heme Biomimetic Cr-N-Tetramethylated Cyclam Complexes

Computational Mechanistic Insights on the NO Oxidation Reaction Catalyzed by Non-Heme Biomimetic Cr-N-Tetramethylated Cyclam Complexes

The conversion reaction of NO to NO<sub>3</sub><sup>&#8722;</sup> ion catalyzed by the end-on [Cr(III)(n-TMC)(O<sub>2</sub>)(Cl)]<sup>+</sup> superoxo and side-on [Cr(IV)(n-TMC)(O<sub>2</sub>)(Cl)]<sup>+</sup> peroxo non-hem...

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Main Authors: Tiziana Marino, Maria Grazia Fortino, Nino Russo, Marirosa Toscano, Marta Erminia Alberto
Format: Article
Language:English
Published: MDPI AG 2019-08-01
Series:International Journal of Molecular Sciences
Subjects:
biomimetic chromium catalysts
DFT
potential energy surface
NO catalytic conversion
Online Access:https://www.mdpi.com/1422-0067/20/16/3955
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spelling doaj-6ae376b562a54bc5b827f748055058b42020-11-25T01:57:09ZengMDPI AGInternational Journal of Molecular Sciences1422-00672019-08-012016395510.3390/ijms20163955ijms20163955Computational Mechanistic Insights on the NO Oxidation Reaction Catalyzed by Non-Heme Biomimetic Cr-N-Tetramethylated Cyclam ComplexesTiziana Marino0Maria Grazia Fortino1Nino Russo2Marirosa Toscano3Marta Erminia Alberto4Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, 87036 Rende, ItalyDipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, 87036 Rende, ItalyDipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, 87036 Rende, ItalyDipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, 87036 Rende, ItalyDipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, 87036 Rende, ItalyThe conversion reaction of NO to NO<sub>3</sub><sup>&#8722;</sup> ion catalyzed by the end-on [Cr(III)(n-TMC)(O<sub>2</sub>)(Cl)]<sup>+</sup> superoxo and side-on [Cr(IV)(n-TMC)(O<sub>2</sub>)(Cl)]<sup>+</sup> peroxo non-heme complexes (<i>n</i> = 12, 13, 14 and 15), which are biomimetic systems of nitric oxide dioxygenases (NODs), has been explored using a computational protocol in the framework of density functional theory. Results show that the potential energy profiles for the studied reactions lie above the reagent energies, regardless of the used catalyst. Both the O-O bond breaking in the biomimetics and the NO<sub>3</sub><sup>&#8722;</sup> ion formation require low energy barriers suggesting an efficient catalytic power of the studied systems. The rate-determining step depends on ligand size.https://www.mdpi.com/1422-0067/20/16/3955biomimetic chromium catalystsDFTpotential energy surfaceNO catalytic conversion
collection DOAJ
language English
format Article
sources DOAJ
author Tiziana Marino
Maria Grazia Fortino
Nino Russo
Marirosa Toscano
Marta Erminia Alberto
spellingShingle Tiziana Marino
Maria Grazia Fortino
Nino Russo
Marirosa Toscano
Marta Erminia Alberto
Computational Mechanistic Insights on the NO Oxidation Reaction Catalyzed by Non-Heme Biomimetic Cr-N-Tetramethylated Cyclam Complexes
International Journal of Molecular Sciences
biomimetic chromium catalysts
DFT
potential energy surface
NO catalytic conversion
author_facet Tiziana Marino
Maria Grazia Fortino
Nino Russo
Marirosa Toscano
Marta Erminia Alberto
author_sort Tiziana Marino
title Computational Mechanistic Insights on the NO Oxidation Reaction Catalyzed by Non-Heme Biomimetic Cr-N-Tetramethylated Cyclam Complexes
title_short Computational Mechanistic Insights on the NO Oxidation Reaction Catalyzed by Non-Heme Biomimetic Cr-N-Tetramethylated Cyclam Complexes
title_full Computational Mechanistic Insights on the NO Oxidation Reaction Catalyzed by Non-Heme Biomimetic Cr-N-Tetramethylated Cyclam Complexes
title_fullStr Computational Mechanistic Insights on the NO Oxidation Reaction Catalyzed by Non-Heme Biomimetic Cr-N-Tetramethylated Cyclam Complexes
title_full_unstemmed Computational Mechanistic Insights on the NO Oxidation Reaction Catalyzed by Non-Heme Biomimetic Cr-N-Tetramethylated Cyclam Complexes
title_sort computational mechanistic insights on the no oxidation reaction catalyzed by non-heme biomimetic cr-n-tetramethylated cyclam complexes
publisher MDPI AG
series International Journal of Molecular Sciences
issn 1422-0067
publishDate 2019-08-01
description The conversion reaction of NO to NO<sub>3</sub><sup>&#8722;</sup> ion catalyzed by the end-on [Cr(III)(n-TMC)(O<sub>2</sub>)(Cl)]<sup>+</sup> superoxo and side-on [Cr(IV)(n-TMC)(O<sub>2</sub>)(Cl)]<sup>+</sup> peroxo non-heme complexes (<i>n</i> = 12, 13, 14 and 15), which are biomimetic systems of nitric oxide dioxygenases (NODs), has been explored using a computational protocol in the framework of density functional theory. Results show that the potential energy profiles for the studied reactions lie above the reagent energies, regardless of the used catalyst. Both the O-O bond breaking in the biomimetics and the NO<sub>3</sub><sup>&#8722;</sup> ion formation require low energy barriers suggesting an efficient catalytic power of the studied systems. The rate-determining step depends on ligand size.
topic biomimetic chromium catalysts
DFT
potential energy surface
NO catalytic conversion
url https://www.mdpi.com/1422-0067/20/16/3955
work_keys_str_mv AT tizianamarino computationalmechanisticinsightsonthenooxidationreactioncatalyzedbynonhemebiomimeticcrntetramethylatedcyclamcomplexes
AT mariagraziafortino computationalmechanisticinsightsonthenooxidationreactioncatalyzedbynonhemebiomimeticcrntetramethylatedcyclamcomplexes
AT ninorusso computationalmechanisticinsightsonthenooxidationreactioncatalyzedbynonhemebiomimeticcrntetramethylatedcyclamcomplexes
AT marirosatoscano computationalmechanisticinsightsonthenooxidationreactioncatalyzedbynonhemebiomimeticcrntetramethylatedcyclamcomplexes
AT martaerminiaalberto computationalmechanisticinsightsonthenooxidationreactioncatalyzedbynonhemebiomimeticcrntetramethylatedcyclamcomplexes
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