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
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|
| dc.title.spa.fl_str_mv |
On the reaction mechanism of the complete intermolecular o2 transfer between mononuclear nickel and manganese complexes with macrocyclic ligands |
| dc.title.translated.spa.fl_str_mv |
Sobre el mecanismo de reacción de la transferencia intermolecular completa de o2 entre los complejos de níquel mononuclear y manganeso con ligandos macrocíclicos |
| title |
On the reaction mechanism of the complete intermolecular o2 transfer between mononuclear nickel and manganese complexes with macrocyclic ligands |
| spellingShingle |
On the reaction mechanism of the complete intermolecular o2 transfer between mononuclear nickel and manganese complexes with macrocyclic ligands 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 |
| title_short |
On the reaction mechanism of the complete intermolecular o2 transfer between mononuclear nickel and manganese complexes with macrocyclic ligands |
| title_full |
On the reaction mechanism of the complete intermolecular o2 transfer between mononuclear nickel and manganese complexes with macrocyclic ligands |
| title_fullStr |
On the reaction mechanism of the complete intermolecular o2 transfer between mononuclear nickel and manganese complexes with macrocyclic ligands |
| title_full_unstemmed |
On the reaction mechanism of the complete intermolecular o2 transfer between mononuclear nickel and manganese complexes with macrocyclic ligands |
| title_sort |
On the reaction mechanism of the complete intermolecular o2 transfer between mononuclear nickel and manganese complexes with macrocyclic ligands |
| dc.creator.fl_str_mv |
Zapata Rivera, Jhon Enrique Caballol, Rosa Jiménez Calzado, Carmen G Liakos, Dimitrios Neese, Frank |
| dc.contributor.author.spa.fl_str_mv |
Zapata Rivera, Jhon Enrique Caballol, Rosa Jiménez Calzado, Carmen G Liakos, Dimitrios Neese, Frank |
| dc.subject.spa.fl_str_mv |
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 |
| topic |
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 |
| description |
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. |
| publishDate |
2014 |
| dc.date.issued.none.fl_str_mv |
2014-10-06 |
| dc.date.accessioned.none.fl_str_mv |
2019-05-17T14:09:10Z |
| dc.date.available.none.fl_str_mv |
2019-05-17T14:09:10Z |
| dc.type.spa.fl_str_mv |
Artículo de revista |
| dc.type.coar.fl_str_mv |
http://purl.org/coar/resource_type/c_2df8fbb1 |
| dc.type.coar.spa.fl_str_mv |
http://purl.org/coar/resource_type/c_6501 |
| dc.type.content.spa.fl_str_mv |
Text |
| dc.type.driver.spa.fl_str_mv |
info:eu-repo/semantics/article |
| dc.type.redcol.spa.fl_str_mv |
http://purl.org/redcol/resource_type/ART |
| dc.type.version.spa.fl_str_mv |
info:eu-repo/semantics/acceptedVersion |
| format |
http://purl.org/coar/resource_type/c_6501 |
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acceptedVersion |
| dc.identifier.issn.spa.fl_str_mv |
0947-6539 |
| dc.identifier.uri.spa.fl_str_mv |
http://hdl.handle.net/11323/4185 |
| dc.identifier.instname.spa.fl_str_mv |
Corporación Universidad de la Costa |
| dc.identifier.reponame.spa.fl_str_mv |
REDICUC - Repositorio CUC |
| dc.identifier.repourl.spa.fl_str_mv |
https://repositorio.cuc.edu.co/ |
| identifier_str_mv |
0947-6539 Corporación Universidad de la Costa REDICUC - Repositorio CUC |
| url |
http://hdl.handle.net/11323/4185 https://repositorio.cuc.edu.co/ |
| dc.language.iso.none.fl_str_mv |
eng |
| language |
eng |
| dc.rights.spa.fl_str_mv |
Attribution-NonCommercial-ShareAlike 4.0 International |
| dc.rights.uri.spa.fl_str_mv |
http://creativecommons.org/licenses/by-nc-sa/4.0/ |
| dc.rights.accessrights.spa.fl_str_mv |
info:eu-repo/semantics/openAccess |
| dc.rights.coar.spa.fl_str_mv |
http://purl.org/coar/access_right/c_abf2 |
| rights_invalid_str_mv |
Attribution-NonCommercial-ShareAlike 4.0 International http://creativecommons.org/licenses/by-nc-sa/4.0/ http://purl.org/coar/access_right/c_abf2 |
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openAccess |
| dc.publisher.spa.fl_str_mv |
Universidad de la Costa |
| institution |
Corporación Universidad de la Costa |
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Zapata Rivera, Jhon Enrique6d429bd90010d26a764d1ed41ffd627eCaballol, Rosa206c191522e8b56d2b529b6d3a16ab5fJiménez Calzado, Carmen264fba358616d92b57184463ab0aefa2G Liakos, Dimitrios8ab274f78304a2e2cc6113abcc763634Neese, Frank49a91728b779cc3d60c6229084a244872019-05-17T14:09:10Z2019-05-17T14:09:10Z2014-10-060947-6539http://hdl.handle.net/11323/4185Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/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.La transferencia de O2 intermolecular recientemente descrita entre el complejo Ni-O2 lateral [(12-TMC) Ni-O2] + y el complejo de manganeso [(14-TMC) Mn] 2+, donde 12-TMC y 14-TMC son Ligandos macrocíclicos de 12 y 14 miembros, 12-TMC = 1,4,7,10-tetrametil-1,4,7,10-tetraazaciclododecano y 14-TMC = 1,4,8,11-tetrametil-1,4 , 8,11-tetraazaciclotetradecano, se estudia mediante métodos DFT. Los cálculos de B3LYP que incluyen correcciones de largo alcance y efectos de solventes se realizan para dilucidar el mecanismo. Se han analizado las superficies de energía potencial (PES) compatibles con diferentes estados electrónicos de los reactivos. Los cálculos confirman una reacción de dos pasos, con un primer paso bimolecular que determina la velocidad y predicen el carácter exotérmico del proceso global. La estabilidad relativa de los productos y la barrera inversa están en línea con el hecho de que no se observa experimentalmente una reacción inversa. Se identifica un intermedio con una coordinación μ-η1: η1-O2 y dos estados de transición en el triplete PES, ligeramente por debajo de los puntos estacionarios correspondientes del quinteto PES, lo que sugiere un cruce entre sistemas antes del primer estado de transición. Los parámetros de activación calculados y las energías relativas de los dos estados de transición y los productos están muy de acuerdo con los datos experimentales. Los cálculos sugieren que un anión superóxido se transfiere durante la reacción.engUniversidad de la CostaAttribution-NonCommercial-ShareAlike 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-sa/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Activation parametersBiomimetic complexesDensity functional calculationsO2 transfer reactionPes analysisParámetros de activaciónComplejos biomimeticosCálculos funcionales de densidadReacción de transferencia de O2Análisis de pesOn the reaction mechanism of the complete intermolecular o2 transfer between mononuclear nickel and manganese complexes with macrocyclic ligandsSobre el mecanismo de reacción de la transferencia intermolecular completa de o2 entre los complejos de níquel mononuclear y manganeso con ligandos macrocíclicosArtículo de revistahttp://purl.org/coar/resource_type/c_6501http://purl.org/coar/resource_type/c_2df8fbb1Textinfo:eu-repo/semantics/articlehttp://purl.org/redcol/resource_type/ARTinfo:eu-repo/semantics/acceptedVersionORIGINALOn the Reaction Mechanism of the Complete Intermolecular O2 Transfer between.pdfOn the Reaction Mechanism of the Complete Intermolecular O2 Transfer between.pdfapplication/pdf284209https://repositorio.cuc.edu.co/bitstream/11323/4185/1/On%20the%20Reaction%20Mechanism%20of%20the%20Complete%20Intermolecular%20O2%20Transfer%20between.pdf78592e4dfaaae2af28cab0783f67a794MD51open accessCC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-81031https://repositorio.cuc.edu.co/bitstream/11323/4185/2/license_rdf934f4ca17e109e0a05eaeaba504d7ce4MD52open accessLICENSElicense.txtlicense.txttext/plain; charset=utf-81748https://repositorio.cuc.edu.co/bitstream/11323/4185/3/license.txt8a4605be74aa9ea9d79846c1fba20a33MD53open accessTHUMBNAILOn the Reaction Mechanism of the Complete Intermolecular O2 Transfer between.pdf.jpgOn the Reaction Mechanism of the Complete Intermolecular O2 Transfer between.pdf.jpgimage/jpeg45194https://repositorio.cuc.edu.co/bitstream/11323/4185/5/On%20the%20Reaction%20Mechanism%20of%20the%20Complete%20Intermolecular%20O2%20Transfer%20between.pdf.jpge1582d77cd13f2af12546096479bf7beMD55open accessTEXTOn the Reaction Mechanism of the Complete Intermolecular O2 Transfer between.pdf.txtOn the Reaction Mechanism of the Complete Intermolecular O2 Transfer between.pdf.txttext/plain1819https://repositorio.cuc.edu.co/bitstream/11323/4185/6/On%20the%20Reaction%20Mechanism%20of%20the%20Complete%20Intermolecular%20O2%20Transfer%20between.pdf.txtc1be99b414d59ade7f3ccf695dd980f7MD56open access11323/4185oai:repositorio.cuc.edu.co:11323/41852023-12-14 15:50:42.722Attribution-NonCommercial-ShareAlike 4.0 International|||http://creativecommons.org/licenses/by-nc-sa/4.0/open accessRepositorio Universidad de La Costabdigital@metabiblioteca.comTk9URTogUExBQ0UgWU9VUiBPV04gTElDRU5TRSBIRVJFClRoaXMgc2FtcGxlIGxpY2Vuc2UgaXMgcHJvdmlkZWQgZm9yIGluZm9ybWF0aW9uYWwgcHVycG9zZXMgb25seS4KCk5PTi1FWENMVVNJVkUgRElTVFJJQlVUSU9OIExJQ0VOU0UKCkJ5IHNpZ25pbmcgYW5kIHN1Ym1pdHRpbmcgdGhpcyBsaWNlbnNlLCB5b3UgKHRoZSBhdXRob3Iocykgb3IgY29weXJpZ2h0Cm93bmVyKSBncmFudHMgdG8gRFNwYWNlIFVuaXZlcnNpdHkgKERTVSkgdGhlIG5vbi1leGNsdXNpdmUgcmlnaHQgdG8gcmVwcm9kdWNlLAp0cmFuc2xhdGUgKGFzIGRlZmluZWQgYmVsb3cpLCBhbmQvb3IgZGlzdHJpYnV0ZSB5b3VyIHN1Ym1pc3Npb24gKGluY2x1ZGluZwp0aGUgYWJzdHJhY3QpIHdvcmxkd2lkZSBpbiBwcmludCBhbmQgZWxlY3Ryb25pYyBmb3JtYXQgYW5kIGluIGFueSBtZWRpdW0sCmluY2x1ZGluZyBidXQgbm90IGxpbWl0ZWQgdG8gYXVkaW8gb3IgdmlkZW8uCgpZb3UgYWdyZWUgdGhhdCBEU1UgbWF5LCB3aXRob3V0IGNoYW5naW5nIHRoZSBjb250ZW50LCB0cmFuc2xhdGUgdGhlCnN1Ym1pc3Npb24gdG8gYW55IG1lZGl1bSBvciBmb3JtYXQgZm9yIHRoZSBwdXJwb3NlIG9mIHByZXNlcnZhdGlvbi4KCllvdSBhbHNvIGFncmVlIHRoYXQgRFNVIG1heSBrZWVwIG1vcmUgdGhhbiBvbmUgY29weSBvZiB0aGlzIHN1Ym1pc3Npb24gZm9yCnB1cnBvc2VzIG9mIHNlY3VyaXR5LCBiYWNrLXVwIGFuZCBwcmVzZXJ2YXRpb24uCgpZb3UgcmVwcmVzZW50IHRoYXQgdGhlIHN1Ym1pc3Npb24gaXMgeW91ciBvcmlnaW5hbCB3b3JrLCBhbmQgdGhhdCB5b3UgaGF2ZQp0aGUgcmlnaHQgdG8gZ3JhbnQgdGhlIHJpZ2h0cyBjb250YWluZWQgaW4gdGhpcyBsaWNlbnNlLiBZb3UgYWxzbyByZXByZXNlbnQKdGhhdCB5b3VyIHN1Ym1pc3Npb24gZG9lcyBub3QsIHRvIHRoZSBiZXN0IG9mIHlvdXIga25vd2xlZGdlLCBpbmZyaW5nZSB1cG9uCmFueW9uZSdzIGNvcHlyaWdodC4KCklmIHRoZSBzdWJtaXNzaW9uIGNvbnRhaW5zIG1hdGVyaWFsIGZvciB3aGljaCB5b3UgZG8gbm90IGhvbGQgY29weXJpZ2h0LAp5b3UgcmVwcmVzZW50IHRoYXQgeW91IGhhdmUgb2J0YWluZWQgdGhlIHVucmVzdHJpY3RlZCBwZXJtaXNzaW9uIG9mIHRoZQpjb3B5cmlnaHQgb3duZXIgdG8gZ3JhbnQgRFNVIHRoZSByaWdodHMgcmVxdWlyZWQgYnkgdGhpcyBsaWNlbnNlLCBhbmQgdGhhdApzdWNoIHRoaXJkLXBhcnR5IG93bmVkIG1hdGVyaWFsIGlzIGNsZWFybHkgaWRlbnRpZmllZCBhbmQgYWNrbm93bGVkZ2VkCndpdGhpbiB0aGUgdGV4dCBvciBjb250ZW50IG9mIHRoZSBzdWJtaXNzaW9uLgoKSUYgVEhFIFNVQk1JU1NJT04gSVMgQkFTRUQgVVBPTiBXT1JLIFRIQVQgSEFTIEJFRU4gU1BPTlNPUkVEIE9SIFNVUFBPUlRFRApCWSBBTiBBR0VOQ1kgT1IgT1JHQU5JWkFUSU9OIE9USEVSIFRIQU4gRFNVLCBZT1UgUkVQUkVTRU5UIFRIQVQgWU9VIEhBVkUKRlVMRklMTEVEIEFOWSBSSUdIVCBPRiBSRVZJRVcgT1IgT1RIRVIgT0JMSUdBVElPTlMgUkVRVUlSRUQgQlkgU1VDSApDT05UUkFDVCBPUiBBR1JFRU1FTlQuCgpEU1Ugd2lsbCBjbGVhcmx5IGlkZW50aWZ5IHlvdXIgbmFtZShzKSBhcyB0aGUgYXV0aG9yKHMpIG9yIG93bmVyKHMpIG9mIHRoZQpzdWJtaXNzaW9uLCBhbmQgd2lsbCBub3QgbWFrZSBhbnkgYWx0ZXJhdGlvbiwgb3RoZXIgdGhhbiBhcyBhbGxvd2VkIGJ5IHRoaXMKbGljZW5zZSwgdG8geW91ciBzdWJtaXNzaW9uLgo= |