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Diastereospecific and Diastereoselective Syntheses of Ruthenium(II) Complexes Using N,N‘ Bidentate Ligands Aryl-pyridin-2-ylmethyl-amine ArNH-CH<sub>2</sub>-2-C<sub>5</sub>H<sub>4</sub>N and Their Oxidation to Imine Ligands

Javier GómezDepartamento de Química, Facultad de Ciencias, Universidad de Burgos, 09001 Burgos, Spain, Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Zaragoza, Zaragoza, Spain, and Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393Gabriel García‐HerbosaDepartamento de Química, Facultad de Ciencias, Universidad de Burgos, 09001 Burgos, Spain, Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Zaragoza, Zaragoza, Spain, and Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393José V. CuevasDepartamento de Química, Facultad de Ciencias, Universidad de Burgos, 09001 Burgos, Spain, Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Zaragoza, Zaragoza, Spain, and Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393Ana ArnáizDepartamento de Química, Facultad de Ciencias, Universidad de Burgos, 09001 Burgos, Spain, Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Zaragoza, Zaragoza, Spain, and Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393Arancha CarbayoDepartamento de Química, Facultad de Ciencias, Universidad de Burgos, 09001 Burgos, Spain, Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Zaragoza, Zaragoza, Spain, and Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393Asunción MuñozDepartamento de Química, Facultad de Ciencias, Universidad de Burgos, 09001 Burgos, Spain, Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Zaragoza, Zaragoza, Spain, and Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393Larry R. FalvelloDepartamento de Química, Facultad de Ciencias, Universidad de Burgos, 09001 Burgos, Spain, Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Zaragoza, Zaragoza, Spain, and Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393Phillip E. FanwickDepartamento de Química, Facultad de Ciencias, Universidad de Burgos, 09001 Burgos, Spain, Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Zaragoza, Zaragoza, Spain, and Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1393
2006en
ABI

Аннотация

Coordination of N,N' bidentate ligands aryl-pyridin-2-ylmethyl-amine ArNH-CH2-2-C5H4N 1 (Ar = 4-CH3-C6H4, 1a; 4-CH3O-C6H4, 1b; 2,6-(CH3)2-C6H3, 1c; 4-CF3-C6H4, 1d) to the moieties [Ru(bipy)2]2+, [Ru(eta5-C5H5)L]+ (L = CH3CN, CO), or [Ru(eta6-arene)Cl]2+ (arene = benzene, p-cymene) occurs under diastereoselective or diastereospecific conditions. Detailed stereochemical analysis of the new complexes is included. The coordination of these secondary amine ligands activates their oxidation to imines by molecular oxygen in a base-catalyzed reaction and hydrogen peroxide was detected as byproduct. The amine-to-imine oxidation was also observed under the experimental conditions of cyclic voltammetry measurements. Deprotonation of the coordinated amine ligands afforded isolatable amido complexes only for the ligand (1-methyl-1-pyridin-2-yl-ethyl)-p-tolyl-amine, 1e, which doesn't contain hydrogen atoms in a beta position relative to the N-H bond. The structures of [Ru(2,2'-bipyridine)2(1b)](PF6)2, 2b; [Ru(2,2'-bipyridine)(2)(1c)](PF6)2, 2c; trans-[RuCl2(COD)(1a)], 3; and [RuCl2(eta6-C6H6)(1a)]PF6, 4a, have been confirmed by X-ray diffraction studies.

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