title: Imido-pyridine Ti(IV) compounds: synthesis of unusual imido-amido heterobimetallic derivatives.
abstract: The reaction of lithiated picolines and [TiCl3(η(5)-C5Me5)] leads to several bridging or terminal imido compounds, each of which can be selectively formed by controlling the stoichiometry and temperature. Specifically, the dinuclear imido-bridged [TiCl(η(5)-C5Me5)(μ-NR)]2 (1a, NR = 2-imido-3-picoline; 1b, NR = 2-imido-5-picoline) species and the unusual Ti-Li imido-amido heterobimetallic complex [{Li(THF)}{Ti(η(5)-C5Me5)(NR)(NHR)2}] (2a, NR = 2-imido-3-picoline; 2b, NR = 2-imido-5-picoline) were isolated. Compounds 2 are in effect the first structurally characterized examples of titanium(IV) coordinated to terminal imido-pyridines. DFT-D calculations for 2a denote a multiple bond character between titanium and the imido ligand and a strong polarization of the electron density by the alkali cation in spite of the lack of intermetallic bonding.
authors.affiliation: Departamento de Química Orgánica y Química Inorgánica, Universidad de Alcalá, Campus Universitario, E-28871 Alcalá de Henares, Spain. pilar.gomez@uah.es martaeg.mosquera@uah.es.
authors.forename: Sergio
authors.initials: S
authors.lastname: Pedrosa
authors.forename: Fernando
authors.initials: F
authors.lastname: Vidal
authors.forename: Lucia Myongwon
authors.initials: LM
authors.lastname: Lee
authors.forename: Ignacio
authors.initials: I
authors.lastname: Vargas-Baca
authors.forename: Pilar
authors.initials: P
authors.lastname: Gómez-Sal
authors.forename: Marta E G
authors.initials: ME
authors.lastname: Mosquera