Synthesis, Characterization, and Theoretical Study of Stable Hydride-Azavinylidene Osmium(IV) Complexes
Autores: Ricardo Castarlenas, Miguel A. Esteruelas, Enrique Gutiérrez-Puebla, Yves Jean, Agustí Lledós, Marta Martín, Enrique Oñate y Jaume Tomás
Ref. revista: Organometallics, 19, 3100-3108, (2000)
The dihydride-dichloro complex OsH2Cl2(PiPr3)2 (1) reacts with cyclohexanone oxime in toluene under reflux to give after 12 h OsHCl2{NdC(CH2)4CH2}(PiPr3)2 (2), which can be also obtained by reaction of the oximate compound, OsH2Cl{k-N,k-O[ONdC(CH2)4CH2]}-(PiPr3)2 (3) with HCl. Complex OsHCl2{NdC(CH3)2}(PiPr3)2 (4) has been similarly prepared
by treatment of compound OsH2Cl{k-N,k-O[ONdC(CH3)2]}(PiPr3)2 (5) with HCl. When the reaction of 1 and cyclohexanone oxime, in toluene under reflux, was quenched after 1 h, a mixture of 1, 2, 3, and the trichloroazavinylidene OsCl3{NdC(CH2)4CH2}(PiPr3)2 (6) was obtained. The structures in the solid state of 2 and 6 have been determined by X-ray diffraction studies. In both cases, the geometry around the metal center can be described as a distorted octahedron with the phosphorus atoms of the phosphines occupying trans positions and the CdN group and the carbon atoms bonded to this group lying in a plane that is parallel to the Cl-Os-Cl plane. CCSD(T)//B3LYP calculations on the model complexes OsXCl2(NdCH2)(PH3)2 [X ) H (2t), X ) Cl (6t)] state that the above-mentioned conformation is 15.3 (2t) or 12.1 (6t) kcal mol-1 more stable than that with the azavinylidene ligand parallel to the P-Os-P plane. In solution the azavinylidene ligands of 2 and 4 rotate around the Os-N-C axis. The activation parameters of the process are ¢Hq ) 14.4 ( 0.8 kcal mol-1 and ¢Sq ) -1.1 ( 1.3 cal mol-1 K-1 for 2 and ¢Hq ) 13.1 ( 0.8 kcal mol-1 and ¢Sq ) 0.0 (2.8 cal mol-1 K-1 for 4.
The dihydride-dichloro complex OsH2Cl2(PiPr3)2 (1) reacts with cyclohexanone oxime in toluene under reflux to give after 12 h OsHCl2{NdC(CH2)4CH2}(PiPr3)2 (2), which can be also obtained by reaction of the oximate compound, OsH2Cl{k-N,k-O[ONdC(CH2)4CH2]}-(PiPr3)2 (3) with HCl. Complex OsHCl2{NdC(CH3)2}(PiPr3)2 (4) has been similarly prepared
by treatment of compound OsH2Cl{k-N,k-O[ONdC(CH3)2]}(PiPr3)2 (5) with HCl. When the reaction of 1 and cyclohexanone oxime, in toluene under reflux, was quenched after 1 h, a mixture of 1, 2, 3, and the trichloroazavinylidene OsCl3{NdC(CH2)4CH2}(PiPr3)2 (6) was obtained. The structures in the solid state of 2 and 6 have been determined by X-ray diffraction studies. In both cases, the geometry around the metal center can be described as a distorted octahedron with the phosphorus atoms of the phosphines occupying trans positions and the CdN group and the carbon atoms bonded to this group lying in a plane that is parallel to the Cl-Os-Cl plane. CCSD(T)//B3LYP calculations on the model complexes OsXCl2(NdCH2)(PH3)2 [X ) H (2t), X ) Cl (6t)] state that the above-mentioned conformation is 15.3 (2t) or 12.1 (6t) kcal mol-1 more stable than that with the azavinylidene ligand parallel to the P-Os-P plane. In solution the azavinylidene ligands of 2 and 4 rotate around the Os-N-C axis. The activation parameters of the process are ¢Hq ) 14.4 ( 0.8 kcal mol-1 and ¢Sq ) -1.1 ( 1.3 cal mol-1 K-1 for 2 and ¢Hq ) 13.1 ( 0.8 kcal mol-1 and ¢Sq ) 0.0 (2.8 cal mol-1 K-1 for 4.