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Synthesis, structure, spectroscopy and reactivity of new heterotrinuclear water oxidation catalysts
Mognon, Lorenzo (Institute of Chemical Research of Catalonia (ICIQ))
Mandal, Sukanta (Institute of Technology Kharagpur. Department of Chemistry)
Castillo, Carmen E. (Centre National de la Recherche Scientifique (CNRS))
Fortage, Jérôme (Centre National de la Recherche Scientifique (CNRS))
Molton, Florian (Centre National de la Recherche Scientifique (CNRS))
Aromí, Guillem (Universitat de Barcelona. Departament de Química Inorgànica)
Benet-Buchhlolz, Jordi (Institute of Chemical Research of Catalonia (ICIQ))
Collomb, Marie-Noëlle (Centre National de la Recherche Scientifique (CNRS))
Llobet Dalmases, Antoni (Universitat Autònoma de Barcelona. Departament de Química)

Fecha: 2016
Resumen: Four heterotrinuclear complexes containing the ligands 3,5-bis(2-pyridyl)pyrazolate (bpp –) and 2,2′:6′,2′′-terpyridine (trpy) of the general formula {[Ru II (trpy)](μ-[M(X)(bpp)])}(PF) have been prepared for the first time. Four heterotrinuclear complexes containing the ligands 3,5-bis(2-pyridyl)pyrazolate (bpp –) and 2,2′:6′,2′′-terpyridine (trpy) of the general formula {[Ru II (trpy)](μ-[M(X)(bpp)])}(PF), where M = Co II, Mn II and X = Cl –, AcO – (M = Co II, X = Cl – : RuCo–Cl ; M = Mn II, X = Cl – : RuMn–Cl ; M = Co II, X = AcO – : RuCo–OAc ; M = Mn II, X = AcO – : RuMn–OAc), have been prepared for the first time. The complexes have been characterized using different spectroscopic techniques such as UV-vis, IR, and mass spectrometry. X-Ray diffraction analyses have been used to characterize the RuMn–Cl and RuMn–OAc complexes. The cyclic voltammograms (CV) for all four complexes in organic solvent (CHCN or CHCl) display three successive reversible oxidative waves corresponding to one-electron oxidations of each of the three metal centers. The oxidized forms of the complexes RuCo–OAc and RuMn–OAc are further characterized by EPR and UV-vis spectroscopy. The magnetic susceptibility measurements of all complexes in the temperature range of 2–300 K reveal paramagnetic properties due to the presence of high spin Co() and Mn() centers. The complexes RuCo–OAc and RuMn–OAc act as precatalysts for the water oxidation reaction, since the acetato groups are easily replaced by water at pH = 7 generating the active catalysts, {[Ru(HO)(trpy)](μ-[M(HO)(bpp)])} 4+ (M = Co II : RuCo–(HO) ; M = Mn II : RuMn–(HO)). The photochemical water oxidation reaction is studied using [Ru(bpy)] 2+ as the photosensitizer and NaSO as a sacrificial electron acceptor at pH = 7. The Co containing complex generates a TON of 50 in about 10 minutes (TOF = 0. 21 s –1), whereas the Mn containing complex only generates a TON of 8. The water oxidation reaction of RuCo–(HO) is further investigated using oxone as a sacrificial chemical oxidant at pH = 7. Labelled water oxidation experiments suggest that a nucleophilic attack mechanism is occurring at the Co site of the trinuclear complex with cooperative involvement of the two Ru sites, via electronic coupling through the bpp – bridging ligand and via neighboring hydrogen bonding.
Nota: Número d'acord de subvenció MINECO/CTQ-2013-49075-R
Nota: Número d'acord de subvenció MINECO/SEV-2013-0319
Nota: Número d'acord de subvenció MINECO/CTQ-2014-52974-REDC
Nota: Número d'acord de subvenció MINECO/ENE-2014-52280-REDT
Nota: Número d'acord de subvenció MINECO/CTQ-2012-32247
Nota: Altres ajuts: EU COST actions CM1202 i CM1205; Labex Arcane (ANR-11-LABX-0003-01)
Derechos: Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original. Creative Commons
Lengua: Anglès.
Documento: article ; recerca ; publishedVersion
Publicado en: Chemical Science, Vol. 7 (february 2016) , p. 3304-3312, ISSN 2041-6539

PMID: 29997822
DOI: 10.1039/c5sc04672f


9 p, 998.5 KB

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