title: Redox-active behavior of the [{Ti(η(5)-C5Me5)(μ-NH)}3(μ3-N)] metalloligand.
abstract: Treatment of [Cl3Y{(μ3-NH)3Ti3(η(5)-C5Me5)3(μ3-N)}] with [K(C5Me5)] in toluene gives C10Me10 and the paramagnetic [K(μ-Cl)3Y{(μ3-NH)3Ti3(η(5)-C5Me5)3(μ3-N)}] (3) derivative. Crystallization of 3 in pyridine affords the potassium-free [Cl2(py)2Y{(μ3-NH)3Ti3(η(5)-C5Me5)3(μ3-N)}] (4) complex. Whereas the reaction of 3 with 1 equiv of 18-crown-6 leads to the molecular complex [(18-crown-6)K(μ-Cl)3Y{(μ3-NH)3Ti3(η(5)-C5Me5)3(μ3-N)}] (5), the analogous treatment of 3 with cryptand-222 affords the ion pair [K(crypt-222)][Cl3Y{(μ3-NH)3Ti3(η(5)-C5Me5)3(μ3-N)}] (6). The X-ray crystal structures of 4, 5, and 6 have been determined. Density functional theory (DFT) calculations have elucidated the electronic structure of these species, which should be regarded as containing trivalent Y bonded to the {(μ3-NH)3Ti3(η(5)-C5Me5)3(μ3-N)} metalloligand radical anion.
authors: Departamento de Química Inorgánica, Universidad de Alcalá, 28871 Alcalá de Henares-Madrid, Spain.
authors: Jorge
authors: J
authors: Caballo
authors: Jorge J
authors: JJ
authors: Carbó
authors: Miguel
authors: M
authors: Mena
authors: Adrián
authors: A
authors: Pérez-Redondo
authors: Josep-M
authors: JM
authors: Poblet
authors: Carlos
authors: C
authors: Yélamos
mesh_terms: D018360:Crystallography, X-Ray; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D014025:Titanium / Q000737:chemistry*
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D014025:Titanium