title: Oxidative Addition of Group 14 Element Hydrido Compounds to OsH(2)(eta(2)-CH(2)=CHEt)(CO)(P(i)Pr(3))(2): Synthesis and Characterization of the First Trihydrido-Silyl, Trihydrido-Germyl, and Trihydrido-Stannyl Derivatives of Osmium(IV).
abstract: The dihydrido-olefin complex OsH(2)(eta(2)-CH(2)=CHEt)(CO)(P(i)Pr(3))(2) (2) reacts with H(2)SiPh(2) to give OsH(3)(SiHPh(2))(CO)(P(i)Pr(3))(2) (3). The molecular structure of 3 has been determined by X-ray diffraction (monoclinic, space group P2(1)/c with a = 16.375(2) Å, b = 11.670(1) Å, c =18.806(2) Å, beta = 107.67(1) degrees, and Z = 4) together with ab initio calculations on the model compound OsH(3)(SiH(3))(CO)(PH(3))(2). The coordination geometry around the osmium center can be rationalized as a heavily distorted pentagonal bipyramid with one hydrido ligand and the carbonyl group in the axial positions. The two other hydrido ligands lie in the equatorial plane, one between the phosphine ligands and the other between the SiHPh(2) group and one of the phosphine ligands. Complex 3 can also be prepared by reaction of OsH(eta(2)-H(2)BH(2))(CO)(P(i)Pr(3))(2) (4) with H(2)SiPh(2). Similarly, the treatment of 4 with HSiPh(3) affords OsH(3)(SiPh(3))(CO)(P(i)Pr(3))(2) (5), while the addition of H(3)SiPh to 4 in methanol yields OsH(3){Si(OMe)(2)Ph}(CO)(P(i)Pr(3))(2) (6). Complex 2 also reacts with HGeR(3) and HSnR(3) to give OsH(3)(GeR(3))(CO)(P(i)Pr(3))(2) (GeR(3) = GeHPh(2) (7), GePh(3) (8), GeEt(3) (9)) and OsH(3)(SnR(3))(CO)(P(i)Pr(3))(2) (R = Ph (10), (n)Bu (11)), respectively. In solution, compounds 3 and 5-11 are fluxional and display similar (1)H and (31)P{(1)H} NMR spectra, suggesting that they possess a similar arrangement of ligands around the osmium atom.
authors.affiliation: Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza, CSIC, 50009 Zaragoza, Spain, Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47005 Valladolid, Spain, and Unitat de Química Física, Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona, Spain.
authors.forename: María L.
authors.initials: ML
authors.lastname: Buil
authors.forename: Pablo
authors.initials: P
authors.lastname: Espinet
authors.forename: Miguel A.
authors.initials: MA
authors.lastname: Esteruelas
authors.forename: Fernando J.
authors.initials: FJ
authors.lastname: Lahoz
authors.forename: Agustí
authors.initials: A
authors.lastname: Lledós
authors.forename: Jesús M.
authors.initials: JM
authors.lastname: Martínez-Ilarduya
authors.forename: Feliu
authors.initials: F
authors.lastname: Maseras
authors.forename: Javier
authors.initials: J
authors.lastname: Modrego
authors.forename: Enrique
authors.initials: E
authors.lastname: Oñate
authors.forename: Luis A.
authors.initials: LA
authors.lastname: Oro
authors.forename: Eduardo
authors.initials: E
authors.lastname: Sola
authors.forename: Cristina
authors.initials: C
authors.lastname: Valero