Reactivity and spectroscopy of the {Ru(DMAP)5} fragment: an {Ru(NH3)5} analogue

M. B. ROSSI; O.E. PIRO; E. E. CASTELLANO; P. ALBORÉS; L. M. BARALDO

INORGANIC CHEMISTRY

American Chemical Society

Año: 2008 vol. 47 p. 2416 - 2427

0020-1669

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]Cl2·6EtOH was determined by X-ray diffraction methods. The complex crystallizes in the trigonal R-3 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 [RuIII(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 {RuII(DMAP)5}fragment is a weaker π-donor than {RuII(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.