Unraveling the Mechanism of Hydrogen Atom Transfer by a Nickel-Hypochlorite Species and the Influence of Electronic Effects

Theoretical calculations show that the active species in C−H hydrogen atom abstraction corresponds to [Ni(O)(HL)]+, formed after homolytic cleavage of the O−Cl bond of the experimentally trapped [Ni(OCl)(HL)]+. Electronic tuning of the macrocyclic ligand has a very modest impact on the reactivity an...

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Detalles Bibliográficos
Autores: Juvanteny i Palomeras, Adrià, Souilah, Charafa, Quintero, Raquel, Garcia Bellido, Carlos, Pagès-Vilà, Neus, Corona Prieto, Teresa, Salvador Sedano, Pedro, Company Casadevall, Anna
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2024
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/25169
Acceso en línea:http://hdl.handle.net/10256/25169
Access Level:acceso abierto
Palabra clave:Quàntums, Teoria dels
Quantum theory
Compostos macrocíclics
Macrocyclic compounds
Lligands
Ligands
Oxidació
Oxidation
Clor
Chlorine
Descripción
Sumario:Theoretical calculations show that the active species in C−H hydrogen atom abstraction corresponds to [Ni(O)(HL)]+, formed after homolytic cleavage of the O−Cl bond of the experimentally trapped [Ni(OCl)(HL)]+. Electronic tuning of the macrocyclic ligand has a very modest impact on the reactivity and stability of the corresponding active species, which show a controversial oxidation state assignment due to the redox noninnocence of the ligands, as ascertained by the effective oxidation state analysis