INQUINOA   21218
INSTITUTO DE QUIMICA DEL NOROESTE
Unidad Ejecutora - UE
artículos
Título:
Structural, Electronic, and Thermochemical Preference for Multi-PCET Reactivity of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes
Autor/es:
CATTANEO, MAURICIO; KAMINSKY, WERNER; TENDERHOLT, ADAM L.; PARADA, GIOVANNY A.; MAYER, JAMES M.
Revista:
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Editorial:
WILEY-V C H VERLAG GMBH
Referencias:
Año: 2021
ISSN:
1434-1948
Resumen:
The multiredox reactivity of bioinorganic cofactors is often coupled to proton transfers. Here we investigate the structural, thermochemical, and electronic structure of ruthenium-amino/amido complexes with multi- proton-coupled electron transfer reactivity. The bis(amino)ruthenium(II) and bis(amido)ruthenium(IV) complexes [RuII(bpy)(en*)2]2+ (RuII-H0) and [RuIV(bpy)(en*-H2)2]2+ (RuIV-H2) interconvert reversibly with the transfer of 2e−/2H+ (bpy=2,2?-bipyridine, en*=2,3-diamino-2,3-dimethylbutane). X-ray structures allow correlations between the structural and electronic parameters, and the thermochemical data of the 2e−/2H+ multi-square grid scheme. Redox potentials, acidity constants and DFT calculations reveal potential intermediates implicated in 2e−/2H+ reactivity with organic reagents in non-protic solvents, which shows a strong inverted redox potential favoring 2e−/2H+ transfer. This is suggested to be an attractive system for potential one-step (concerted) transfer of 2e−and 2H+ due to the small changes of the pseudo-octahedral geometries and the absence of charge change, indicating a relatively small overall reorganization energy.