title: Bis(allyl)ruthenium(IV) complexes containing water-soluble phosphane ligands: synthesis, structure, and application as catalysts in the selective hydration of organonitriles into amides.
abstract: The novel mononuclear ruthenium(IV) complexes [RuCl(2)(eta(3):eta(3)-C(10)H(16))(L)] [L=(meta-sulfonatophenyl)diphenylphosphane sodium salt (TPPMS) (2a), 1,3,5-triaza-7-phosphatricyclo[3.3.1.1(3, 7)]decane (PTA) (2b), 1-benzyl-3,5-diaza-1-azonia-7-phosphatricyclo[3.3.1.1(3, 7)]decane chloride (PTA-Bn) (2c), 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) (2d), and 2,4,10-trimethyl-1,2,4,5,7,10-hexaaza-3-phosphatricyclo[3.3.1.1(3, 7)]decane (THPA) (2e)] have been synthesized by treatment of the dimeric precursor [{RuCl(mu-Cl)(eta(3):eta(3)-C(10)H(16))}(2)] (C(10)H(16)=2,7-dimethylocta-2,6-diene-1,8-diyl) (1) with two equivalents of the corresponding water-soluble phosphane. Reaction of 1 with one equivalent of the cage-type diphosphane ligand 2,3,5,6,7,8-hexamethyl-2,3,5,6,7,8-hexaaza-1,4-diphosphabicyclo[2.2.2]octane (THDP) allowed also the high-yield preparation of the dinuclear derivative [{RuCl(2)(eta(3):eta(3)-C(10)H(16))}(2)(mu-THDP)] (2f). All these new complexes have been analytically and spectroscopically (IR and multinuclear NMR) characterized. In addition, the structure of 2b, 2c, 2d, and 2f was unequivocally confirmed by X-ray diffraction methods. Complexes 2a-f are active catalysts for the selective hydration of nitriles to amides in pure aqueous medium under neutral conditions. The wide scope of this catalytic transformation has been evaluated by using the most active catalysts [RuCl(2)(eta(3):eta(3)-C(10)H(16))(THPA)] (2e) and [{RuCl(2)(eta(3):eta(3)-C(10)H(16))}(2)(mu-THDP)] (2f). Advantages of using MW versus conventional thermal heating are also discussed.
authors.affiliation: Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química Organometálica, Enrique Moles (Unidad Asociada al CSIC), Universidad de Oviedo, Julián Clavería 8, 33006 Oviedo, Spain. vcm@uniovi.es
authors.forename: Victorio
authors.initials: V
authors.lastname: Cadierno
authors.forename: Josefina
authors.initials: J
authors.lastname: Díez
authors.forename: Javier
authors.initials: J
authors.lastname: Francos
authors.forename: José
authors.initials: J
authors.lastname: Gimeno
mesh_terms: D000577:Amides / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D008024:Ligands; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010720:Phosphines / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D012995:Solubility; D013237:Stereoisomerism; D014867:Water
chemical_list: D000577:Amides; D008024:Ligands; D009570:Nitriles; D009942:Organometallic Compounds; D010720:Phosphines; D014867:Water; D012428:Ruthenium; C044646:phosphine