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  On the Reaction Mechanism of the Complete Intermolecular O2 Transfer between Mononuclear Nickel and Manganese Complexes with Macrocyclic Ligands

Zapata-Rivera, J., Caballol, R., Calzado, C. J., Liakos, D. G., & Neese, F. (2014). On the Reaction Mechanism of the Complete Intermolecular O2 Transfer between Mononuclear Nickel and Manganese Complexes with Macrocyclic Ligands. Chemistry – A European Journal, 20(41), 13296-13304. doi:10.1002/chem.201403233.

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Zapata-Rivera, Jhon1, Author
Caballol, Rosa1, Author
Calzado, Carmen J.2, Author
Liakos, Dimitrios G.3, Author              
Neese, Frank3, Author              
Affiliations:
1Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel⋅lí Domingo, s/n, 43007 Tarragona (Spain), ou_persistent22              
2Departamento de Química Física, Universidad de Sevilla c/Profesor García González s/n, 41012, Sevilla (Spain), ou_persistent22              
3Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              

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Free keywords: activation parameters; biomimetic complexes; density functional calculations; O2 transfer reaction; PES analysis
 Abstract: The recently described intermolecular O2 transfer between the side‐on Ni‐O2 complex [(12‐TMC)Ni‐O2]+ and the manganese complex [(14‐TMC)Mn]2+, where 12‐TMC and 14‐TMC are 12‐ and 14‐membered macrocyclic ligands, 12‐TMC=1,4,7,10‐tetramethyl‐1,4,7,10‐tetraazacyclododecane and 14‐TMC=1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclotetradecane, is studied by means of DFT methods. B3LYP calculations including long‐range corrections and solvent effects are performed to elucidate the mechanism. The potential energy surfaces (PESs) compatible with different electronic states of the reactants have been analyzed. The calculations confirm a two‐step reaction, with a first rate‐determining bimolecular step and predict the exothermic character of the global process. The relative stability of the products and the reverse barrier are in line with the fact that no reverse reaction is experimentally observed. An intermediate with a μ‐η11‐O2 coordination and two transition states are identified on the triplet PES, slightly below the corresponding stationary points of the quintet PES, suggesting an intersystem crossing before the first transition state. The calculated activation parameters and the relative energies of the two transition sates and the products are in very good agreement with the experimental data. The calculations suggest that a superoxide anion is transferred during the reaction.

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Language(s): eng - English
 Dates: 2014-09-012014-10-06
 Publication Status: Published in print
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/chem.201403233
 Degree: -

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Title: Chemistry – A European Journal
  Other : Chem. – Eur. J.
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 20 (41) Sequence Number: - Start / End Page: 13296 - 13304 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058