On the reaction mechanism of the complete intermolecular o2 transfer between mononuclear nickel and manganese complexes with macrocyclic ligands
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-tetrameth...
- Autores:
-
Zapata Rivera, Jhon Enrique
Caballol, Rosa
Jiménez Calzado, Carmen
G Liakos, Dimitrios
Neese, Frank
- Tipo de recurso:
- Article of journal
- Fecha de publicación:
- 2014
- Institución:
- Corporación Universidad de la Costa
- Repositorio:
- REDICUC - Repositorio CUC
- Idioma:
- eng
- OAI Identifier:
- oai:repositorio.cuc.edu.co:11323/4185
- Acceso en línea:
- http://hdl.handle.net/11323/4185
https://repositorio.cuc.edu.co/
- Palabra clave:
- Activation parameters
Biomimetic complexes
Density functional calculations
O2 transfer reaction
Pes analysis
Parámetros de activación
Complejos biomimeticos
Cálculos funcionales de densidad
Reacción de transferencia de O2
Análisis de pes
- Rights
- openAccess
- License
- Attribution-NonCommercial-ShareAlike 4.0 International
| Summary: | 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-η1:η1-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. |
|---|