INVESTIGADORES
BARALDO VICTORICA Luis Mario
artículos
Título:
Reactivity and Spectroscopy of the {Ru(DMAP)5} Fragment: An {Ru(NH3)5} Analogue
Autor/es:
MELINA B. ROSSI; OSCAR E. PIRO; EDUARDO E. CASTELLANO; PABLO ALBORÉS; LUIS M. BARALDO
Revista:
INORGANIC CHEMISTRY
Editorial:
American Chemical Society
Referencias:
Lugar: Washington; Año: 2008 vol. 47 p. 2416 - 2427
ISSN:
0020-1669
Resumen:
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) A, gamma = 120 degrees , 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 [Ru(III)(NH3)5Cl](2+) and allows the preparation of a family of [Ru(DMAP)5L](n+) complexes. Their electronic properties indicate that the {Ru(II)(DMAP)5} fragment is a weaker pi-donor than {Ru(II)(NH 3)5}. Our density functional theory (DFT) calculations show that in {Ru(II)(DMAP)5} the DMAP ligands can compete for the pi electron density of the ruthenium making the fragment a weaker pi-donor.
