Artículo
Theoretical and experimental studies of diruthenium tetracarboxylates structure, spectroscopy, and electrochemistry
Fecha de publicación:
06/2008
Editorial:
American Chemical Society
Revista:
Inorganic Chemistry
ISSN:
0020-1669
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
Quantum mechanical calculations at the density functional theory (DFT) level have been performed on diruthenium tetracarboxylates of different levels of molecular complexity: from unsolvated monomers to oligomers. The agreement between the calculated and experimental molecular structures and vibrational modes of the simple [Ru 2 (μ-O 2 CCH 3 ) 4 ] 0/ +and [Ru 2 (μ-O 2 CCH 3 ) 4 (H 2 O) 2 ] 10/+ systems made us confident in our calculation methodology. Therefore, it has been applied to the analysis of two different kinds of properties of these compounds: the trends in the UV/vis spectroscopy and electrochemistry along the [Ru 2 (μ-O 2 CCH 3 ) 4 X 2 ] - (X = Cl - , Br - , I) series, and the crystalline polymorphism related to the polymeric strand conformation in extended Ru 2 (μ-O 2 CR) 4 Cl compounds. For the [Ru 2 (μ-O 2 CCH 3 ) 4 X 2 ] - series, we report new spectroscopic and electrochemical results and interpret the trends on the basis of time dependent DFT-polarized continuum model calculations, local charge and spin analysis, and X donor properties. As far as the polymeric conformation is concerned, it has been previously suggested that the Ru-Cl-Ru angle results from a compromise between packing, orbital overlap, and microsegregation. Our calculations on [RU 2 (μ-O 2 CCH 3 ) 4 Cl] 2 Cl - and [Ru 2 (μ-O 2 CCH 3 ) 4 Cl] 3 Cl - oligomers provide insights on the influence of the first two factors on the strand conformation and allows a suggestion on what is the equatorial aliphatic chain's influence on this issue.
Palabras clave:
Dft
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Articulos(INQUIMAE)
Articulos de INST.D/QUIM FIS D/L MATERIALES MEDIOAMB Y ENERGIA
Articulos de INST.D/QUIM FIS D/L MATERIALES MEDIOAMB Y ENERGIA
Citación
Castro, Maria Ana; Roitberg, Adrián; Cukiernik, Fabio Daniel; Theoretical and experimental studies of diruthenium tetracarboxylates structure, spectroscopy, and electrochemistry; American Chemical Society; Inorganic Chemistry; 47; 11; 6-2008; 4682-4690
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