title: Stimuli-Responsive Frustrated Lewis-Pair-Type Reactivity of a Tungsten Iminoazaphosphiridine Complex.
abstract: Reactions of 3-imino-azaphosphiridine complexes 1 a,b with carbodiimides 2 a,b, isocyanates 3 a,b, and carbon dioxide are described. Whereas exchange of the carbodiimide unit occurs in the first case, an overall ring expansion takes place with phenyl isocyanate (3 a) and carbon dioxide to yield complexes 4 and 5 bearing novel 1,3,5-oxazaphospholane ligands; the isopropyl derivative 3 b did not react under these conditions. DFT calculations provide insight into the pathway of the reaction with carbon dioxide with model complex 1 c, revealing effects of initial non-covalent interactions with the substrate onto the ring bonding, thus triggering an initially masked frustrated Lewis-pair-type behavior.
authors.affiliation: Institut für Anorganische Chemie, Reinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany), Fax:(+49) 228-739616.
authors.forename: José Manuel
authors.initials: JM
authors.lastname: Villalba Franco
authors.affiliation: Institut für Anorganische Chemie, Reinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany), Fax:(+49) 228-739616.
authors.forename: Gregor
authors.initials: G
authors.lastname: Schnakenburg
authors.affiliation: Institut for Chemical Research, Kyoto University, Gokasho Uji, Kyoto, 611-0011 (Japan).
authors.forename: Takahiro
authors.initials: T
authors.lastname: Sasamori
authors.affiliation: Departamento de Química Orgánica, Universidad de Murcia, Campus de Espinardo, 30100 Murcia (Spain), Fax:(+34) 868-884149. artuesp@um.es.
authors.forename: Arturo
authors.initials: A
authors.lastname: Espinosa Ferao
authors.affiliation: Institut für Anorganische Chemie, Reinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany), Fax:(+49) 228-739616. r.streubel@uni-bonn.de.
authors.forename: Rainer
authors.initials: R
authors.lastname: Streubel
keywords: azaphosphiridines; carbodiimides; carbon dioxide; frustrated Lewis pairs; phosphorus