English   español  
Por favor, use este identificador para citar o enlazar a este item: http://hdl.handle.net/10261/133862
Compartir / Impacto:
Estadísticas
Add this article to your Mendeley library MendeleyBASE
Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL
Título

Synthesis, reactivity, and catalytic activity of triangular ZrM2 (M = Rh, Ir) early-late heterobimetallic complexes

AutorHernandez-Gruel, Marc A. F.; Pérez-Torrente, Jesús J. ; Ciriano, Miguel A. ; Rivas, Angel B.; Lahoz, Fernando J. ; Dobrinovich, Isabel T.; Oro, Luis A.
Fecha de publicación2003
EditorAmerican Chemical Society
CitaciónOrganometallics 22(6): 1237-1249 (2003)
ResumenReactions of the zirconium−sulfide metallocene anion [Cptt2ZrS2]2- (Cptt = η5-1,3-di-tert-butylcyclopentadienyl) with [{M(μ-Cl)(diolefin)}2 gave the d0−d8 complexes [Cptt2Zr(μ3-S)2{M(diolefin)}2] (M = Rh, diolefin = 2,5-norbornadiene (nbd) (1), 1,5-cyclooctadiene (cod); M = Ir, diolefin = cod) with a triangular ZrM2 core capped by two symmetrical μ3-sulfido ligands. The rhodium complexes [Cptt2Zr(μ3-S)2{Rh(diolefin)}2] (diolefin = tetrafluorobenzobarrelene (tfbb), nbd, cod) can also be prepared by the additive-deprotonation reactions of the mononuclear [Rh(acac)(diolefin)] (diolefin = nbd, tfbb) and the dinuclear [{Rh(μ-OH)(cod)}2] complexes with [Cptt2Zr(SH)2]. These compounds exist as two rotamers in solution due to a hindered rotation of the cyclopentadienyl rings and the relative disposition of the substituents of the Cptt groups in the sandwich moiety. The reaction of [Cptt2Zr(SH)2] with [Ir(acac)(cod)] gave the complex [Cptt(acac)Zr(μ3-S)2{Ir(cod)}2] (5) with release of HCptt and coordination of acetylacetonate to the zirconium center. Carbonylation of compounds 1 and 5 yielded [Cptt2Zr(μ3-S)2{Rh(CO)2}2] (6) and [Cptt(acac)Zr(μ3-S)2{Ir(CO)2}2], respectively, while the complexes [Cptt2Zr(μ3-S)2{M(CO)2}2] (M = Rh, Ir) resulted also from the reaction of [Cptt2Zr(SH)2] with (PPh3Bz)[MCl2(CO)2] in the presence of triethylamine. Reactions of the carbonyl complexes with 1 molar equiv of bis(diphenylphosphino)methane (dppm) gave the cisoid complexes [Cptt2Zr(μ3-S)2{M(CO)}2(μ-dppm)] (M = Rh (9), Ir) with evolution of carbon monoxide. Monodentate phosphites, P(OMe)3 and P(OPh)3, react with 6 to give mixtures of the transoid and cisoid isomers [Cptt2Zr(μ3-S)2{Rh(CO)(P(OR)3)}2], which also exhibit a restricted rotation of the Cptt rings. The molecular structures of complexes 6 and 9 have been determined by X-ray diffraction methods. Compound 6 in the presence of P-donor ligands, P(OMe)3, P(OPh)3, and PPh3, is a precursor of the catalyst for the hydroformylation of oct-1-ene under mild conditions of pressure and temperature. No Zr−Rh synergic effect is observed in this case, and the precursor breaks down after catalysis.
Versión del editorhttp://dx.doi.org/10.1021/om0209576
URIhttp://hdl.handle.net/10261/133862
DOI10.1021/om0209576
Identificadoresdoi: 10.1021/om0209576
issn: 0276-7333
e-issn: 1520-6041
Aparece en las colecciones: (ICMA) Artículos
Ficheros en este ítem:
Fichero Descripción Tamaño Formato  
Heterobimetallic Complexes.pdf1,53 MBAdobe PDFVista previa
Visualizar/Abrir
Mostrar el registro completo
 

Artículos relacionados:


NOTA: Los ítems de Digital.CSIC están protegidos por copyright, con todos los derechos reservados, a menos que se indique lo contrario.