Reactivity and spectroscopy of the {Ru(DMAP)5} fragment: An {Ru(NH3)5} analogue
Reaction of trans-Ru(DMSO)4Cl2 with DMAP (DMAP = 4-dimethylaminopyridine) yields the yellow [Ru(DMAP)6]2+ cation in good yield. The crystal and molecular structure of [Ru(DMAP) 6]Cl2·6CH3CH2OH was determined by X-ray diffraction methods. The complex crystallizes in the trigonal R3 space group with a...
| Autores: | , , , , |
|---|---|
| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2008 |
| País: | Argentina |
| Institución: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repositorio: | CONICET Digital (CONICET) |
| Idioma: | inglés |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/83774 |
| Acceso en línea: | http://hdl.handle.net/11336/83774 |
| Access Level: | acceso abierto |
| Palabra clave: | Dmap Dft Ruthenium Electronic Spectroscopy https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| Sumario: | Reaction of trans-Ru(DMSO)4Cl2 with DMAP (DMAP = 4-dimethylaminopyridine) yields the yellow [Ru(DMAP)6]2+ cation in good yield. The crystal and molecular structure of [Ru(DMAP) 6]Cl2·6CH3CH2OH was determined by X-ray diffraction methods. The complex crystallizes in the trigonal R3 space group with a = b = 16.373(1), c = 20.311(1) Å, γ = 120°, and Z = 3 molecules per unit cell. The reaction of [Ru(DMAP) 6]2+ in aerobic water gives the red [Ru III(DMAP)5(OH)]2+ cation. This complex shows a chemical behavior similar to [RuIII(NH3) 5Cl]2+ and allows the preparation of a family of [Ru(DMAP)5L]n+ complexes. Their electronic properties indicate that the {RuIII(DMAP)5} fragment is a weaker π-donor than {RuIII(NH3)5}. Our density functional theory (DFT) calculations show that in {RuII(DMAP) 5} the DMAP ligands can compete for the π electron density of the ruthenium making the fragment a weaker π-donor. |
|---|