Premium
Proton‐Coupled Redox Chemistry, Oxidative Reactivity, and Electronic Characterization of Aqua‐, Hydroxo‐, and Oxo‐Triruthenium Clusters
Author(s) -
Nunes Genebaldo S.,
Alexiou Anamaria D. P.,
Araki Koiti,
Formiga André L. B.,
Rocha Reginaldo C.,
Toma Henrique E.
Publication year - 2006
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200501089
Subject(s) - chemistry , deprotonation , pourbaix diagram , protonation , redox , dimer , reactivity (psychology) , cluster (spacecraft) , proton , pyridine , electrochemistry , catalysis , crystallography , inorganic chemistry , photochemistry , medicinal chemistry , ion , organic chemistry , medicine , physics , alternative medicine , electrode , pathology , quantum mechanics , computer science , programming language
The pH‐dependent electronic and electrochemical properties of a series of triangular μ 3 ‐oxo‐centered trinuclear clusters of the type [Ru 3 O(Ac) 6 (py) 2 (OH x )] n (Ac = acetate; py = pyridine; x = 0, 1, or 2; where the formal oxidation states on the metal ions range from +II to +IV) have been investigated with emphasis on the elucidation of the successive proton‐coupled redox processes spanning the interconvertible aqua‐ ( x = 2), hydroxo‐ ( x = 1), and oxo‐ ( x = 0) forms, from which the complete Pourbaix diagram has been proposed. From the spontaneous slow coupling reaction of the monomeric cluster in its deprotonated (oxo) form at high pH, the μ‐oxo‐bridged cluster dimer (i.e. {(py) 2 (Ac) 6 ORu 3 }‐O‐{Ru 3 O(Ac) 6 (py) 2 }) has been isolated and fully characterized by spectroelectrochemistry as well. A further understanding of the underlying electronic interactions across the various oxidation and protonation states, and the role of such phenomena in the activation of the Ru–O bonding system in oxygen‐transfer catalysis, have also been explored. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)