A new dinuclear Ru-Hbpp based water oxidation catalyst with a trans-disposition of the Ru-OH

Joaquim Mola; Chiara Dinoi; Xavier Sala; Montserrat Rodríguez; Isabel Romero; Teodor Parella; Xavier Fontrodona; Antoni Llobet

doi:10.1039/c0dt00964d

A new dinuclear Ru-Hbpp based water oxidation catalyst with a trans-disposition of the Ru-OH

Joaquim Mola, Chiara Dinoi, Xavier Sala, Montserrat Rodríguez, Isabel Romero, Teodor Parella, Xavier Fontrodona, Antoni Llobet

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El lligand bis(2-piridil)etilamina (bpea) s'ha usat com a material de partida per a la síntesi de complexos dinuclears de Ru amb fórmula general trans, fac-([RunX(bpea)]2(μ-bpp))m+ (on X = Cl, n = II, m = 1, trans-RuII-Cl, 1 +; on X = OH, n = III, m = 3, trans-RuIII-OH, 2 3+) en què l'anió pirazolat aniònic bis(2-piridil) (bpp) actua com a lligand dinucleant facial i els ligands monodentats X estan disposats de manera trans amb relació als altres. Aquests complexos s'han caracteritzat per espectroscòpia 1D i 2D NMR, tècniques UV-vis i electroquímiques en solució i anàlisi de difracció de raigs X en estat sòlid. La reacció d'1(PF6) amb Ag+ genera el corresponent complex solvatat on l'anió Cl s'ha eliminat com a AgCl insoluble seguit per oxidació del Ru(ii) a Ru(iii) per generar el corresponent complex dinuclear trans-RuIII-OH, 2(PF6)3. Aquest últim ha demostrat catalitzar l'oxidació de l'aigua en oxigen molecular usant Ce(iv) com a oxidant. L'evolució quantitativa del gas en funció del temps s'ha monitoritzat tant per manometria com per tècniques d'espectroscòpia (MS). Les velocitats inicials relatives de la formació d'oxigen, juntament amb les consideracions estructurals, descarten una ruta de reacció intramolecular O-O. © 2011 The Royal Society of Chemistry.

Idioma original	Anglès
Pàgines (de-a)	3640-3646
Revista	Journal of the Chemical Society. Dalton Transactions
Volum	40
Número	14
DOIs	https://doi.org/10.1039/c0dt00964d
Estat de la publicació	Publicada - 22 de març 2011

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10.1039/c0dt00964d

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https://www.scopus.com/pages/publications/79953904514

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@article{7216e83cebba4370a24a782f0a2a24bf,

title = "A new dinuclear Ru-Hbpp based water oxidation catalyst with a trans-disposition of the Ru-OH",

abstract = "The bis(2-pyridyl)ethylamine (bpea) ligand has been used as a starting material for the synthesis of dinuclear Ru complexes of general formula trans, fac-([RunX(bpea)]2(μ-bpp))m+ (for X = Cl, n = II, m = 1, trans-RuII-Cl, 1 +; for X = OH, n = III, m = 3, trans-RuIII-OH, 2 3+) where the 3,5-bis(2-pyridyl)pyrazolate anionic ligand (bpp) acts as bridging dinucleating ligand, the bpea ligand coordinates in a facial manner and the monodentate ligands X are situated in a trans fashion with regard to one another. These complexes have been characterized in solution by 1D and 2D NMR spectroscopy, UV-vis and electrochemical techniques and in the solid state by X-ray diffraction analysis. The reaction of 1(PF6) with Ag+ generates the corresponding solvated complex where the Cl ligand has been removed as insoluble AgCl, followed by the oxidation of Ru(ii) to Ru(iii) to generate the corresponding dinuclear complex trans-RuIII-OH, 2(PF6)3. The latter has been shown to catalytically oxidize water to molecular dioxygen using Ce(iv) as oxidant. Quantitative gas evolution as a function of time has been monitored on line by both manometry and mass spectroscopy (MS) techniques. Relative initial velocities of oxygen formation together with structural considerations rule out an intramolecular O–O bond formation pathway. {\textcopyright} 2011 The Royal Society of Chemistry.",

author = "Joaquim Mola and Chiara Dinoi and Xavier Sala and Montserrat Rodr{\'i}guez and Isabel Romero and Teodor Parella and Xavier Fontrodona and Antoni Llobet",

year = "2011",

month = mar,

day = "22",

doi = "10.1039/c0dt00964d",

language = "English",

volume = "40",

pages = "3640--3646",

number = "14",

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TY - JOUR

T1 - A new dinuclear Ru-Hbpp based water oxidation catalyst with a trans-disposition of the Ru-OH

AU - Mola, Joaquim

AU - Dinoi, Chiara

AU - Sala, Xavier

AU - Rodríguez, Montserrat

AU - Romero, Isabel

AU - Parella, Teodor

AU - Fontrodona, Xavier

AU - Llobet, Antoni

PY - 2011/3/22

Y1 - 2011/3/22

N2 - The bis(2-pyridyl)ethylamine (bpea) ligand has been used as a starting material for the synthesis of dinuclear Ru complexes of general formula trans, fac-([RunX(bpea)]2(μ-bpp))m+ (for X = Cl, n = II, m = 1, trans-RuII-Cl, 1 +; for X = OH, n = III, m = 3, trans-RuIII-OH, 2 3+) where the 3,5-bis(2-pyridyl)pyrazolate anionic ligand (bpp) acts as bridging dinucleating ligand, the bpea ligand coordinates in a facial manner and the monodentate ligands X are situated in a trans fashion with regard to one another. These complexes have been characterized in solution by 1D and 2D NMR spectroscopy, UV-vis and electrochemical techniques and in the solid state by X-ray diffraction analysis. The reaction of 1(PF6) with Ag+ generates the corresponding solvated complex where the Cl ligand has been removed as insoluble AgCl, followed by the oxidation of Ru(ii) to Ru(iii) to generate the corresponding dinuclear complex trans-RuIII-OH, 2(PF6)3. The latter has been shown to catalytically oxidize water to molecular dioxygen using Ce(iv) as oxidant. Quantitative gas evolution as a function of time has been monitored on line by both manometry and mass spectroscopy (MS) techniques. Relative initial velocities of oxygen formation together with structural considerations rule out an intramolecular O–O bond formation pathway. © 2011 The Royal Society of Chemistry.

AB - The bis(2-pyridyl)ethylamine (bpea) ligand has been used as a starting material for the synthesis of dinuclear Ru complexes of general formula trans, fac-([RunX(bpea)]2(μ-bpp))m+ (for X = Cl, n = II, m = 1, trans-RuII-Cl, 1 +; for X = OH, n = III, m = 3, trans-RuIII-OH, 2 3+) where the 3,5-bis(2-pyridyl)pyrazolate anionic ligand (bpp) acts as bridging dinucleating ligand, the bpea ligand coordinates in a facial manner and the monodentate ligands X are situated in a trans fashion with regard to one another. These complexes have been characterized in solution by 1D and 2D NMR spectroscopy, UV-vis and electrochemical techniques and in the solid state by X-ray diffraction analysis. The reaction of 1(PF6) with Ag+ generates the corresponding solvated complex where the Cl ligand has been removed as insoluble AgCl, followed by the oxidation of Ru(ii) to Ru(iii) to generate the corresponding dinuclear complex trans-RuIII-OH, 2(PF6)3. The latter has been shown to catalytically oxidize water to molecular dioxygen using Ce(iv) as oxidant. Quantitative gas evolution as a function of time has been monitored on line by both manometry and mass spectroscopy (MS) techniques. Relative initial velocities of oxygen formation together with structural considerations rule out an intramolecular O–O bond formation pathway. © 2011 The Royal Society of Chemistry.

UR - https://www.scopus.com/pages/publications/79953904514

U2 - 10.1039/c0dt00964d

DO - 10.1039/c0dt00964d

M3 - Article

SN - 1477-9226

VL - 40

SP - 3640

EP - 3646

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

IS - 14

ER -

A new dinuclear Ru-Hbpp based water oxidation catalyst with a trans-disposition of the Ru-OH

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