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 = 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.
Rossi
Melina B
MB
Departamento de Química Inorgánica, Analítica y Química Física, INQUIMAE, Facultad de Ciencias Exactas y Naturales Universidad de Buenos Aires, Pabellón 2, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina.
Piro
Oscar E
OE
Castellano
Eduardo E
EE
Alborés
Pablo
P
Baraldo
Luis M
LM