title: Unmasking the Action of Phosphinous Acid Ligands in Nitrile Hydration Reactions Catalyzed by Arene-Ruthenium(II) Complexes.
abstract: The catalytic hydration of benzonitrile and acetonitrile has been studied by employing different arene-ruthenium(II) complexes with phosphinous (PR2OH) and phosphorous acid (P(OR)2OH) ligands as catalysts. Marked differences in activity were found, depending on the nature of both the P-donor and η(6)-coordinated arene ligand. Faster transformations were always observed with the phosphinous acids. DFT computations unveiled the intriguing mechanism of acetonitrile hydration catalyzed by these arene-ruthenium(II) complexes. The process starts with attack on the nitrile carbon atom of the hydroxyl group of the P-donor ligand instead of on a solvent water molecule, as previously suggested. The experimental results presented herein for acetonitrile and benzonitrile hydration catalyzed by different arene-ruthenium(II) complexes could be rationalized in terms of such a mechanism.
authors.affiliation: Laboratorio de Compuestos Organometálicos y, Catálisis (Unidad Asociada al CSIC), Centro de Innovación en Química Avanzada (ORFEO-CINQA) and, Departamento de Química Orgánica e Inorgánica, Universidad de Oviedo, Julián Clavería 8, 33006 Oviedo (Spain).
authors.forename: Eder
authors.initials: E
authors.lastname: Tomás-Mendivil
authors.affiliation: Laboratorio de Compuestos Organometálicos y, Catálisis (Unidad Asociada al CSIC), Centro de Innovación en Química Avanzada (ORFEO-CINQA) and, Departamento de Química Orgánica e Inorgánica, Universidad de Oviedo, Julián Clavería 8, 33006 Oviedo (Spain). vcm@uniovi.es.
authors.forename: Victorio
authors.initials: V
authors.lastname: Cadierno
authors.affiliation: Departamento de Química Física y Analítica, Universidad de Oviedo, Julián Clavería 8, 33006 Oviedo (Spain).
authors.forename: María I
authors.initials: MI
authors.lastname: Menéndez
authors.affiliation: Departamento de Química Física y Analítica, Universidad de Oviedo, Julián Clavería 8, 33006 Oviedo (Spain). rlopez@uniovi.es.
authors.forename: Ramón
authors.initials: R
authors.lastname: López
keywords: P ligands; density functional calculations; homogeneous catalysis; reaction mechanisms; ruthenium