Six-coordinate Alkynyldiphenylphosphine Ruthenium (II) Complexes: Synthesis, Structure and Catalytic Activity as ROMP Initiators

  1. Bernechea, M. 1
  2. Lugan, N. 2
  3. Gil, B. 1
  4. Lalinde, E. 1
  5. Lavigne, G. 2
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Laboratoire de Chimie de Coordination, CNRS, 205 Route de Narbonne, 31077 Toulouse Cedex 4, France
Revista:
Organometallics

ISSN: 0276-7333

Año de publicación: 2006

Volumen: 25

Número: 3

Páginas: 684-692

Tipo: Artículo

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DOI: 10.1021/OM050935U SCOPUS: 2-s2.0-33644542784 WoS: WOS:000234906900019 DIALNET GOOGLE SCHOLAR

Otras publicaciones en: Organometallics

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Resumen

Six-coordinate [trans-RuCl2(PPh2C≡CR) 4] (R = Ph (1), (4-CH3)C6H4 (2), (4-OCH3)C6H4, (3), (4-CF3)C 6H4 (4)) were obtained from the reaction of RuCl 3·xH2O with the appropriate alkynylphosphine (PPh2C≡CR) in ethanol. An X-ray crystal structure analysis of 1·4H2O reveals that the complex is obtained as the trans isomer, with the halides occupying apical positions and the phosphorus atoms lying in the equatorial plane. The alkynyl substituents of adjacent P ligands are alternatively pointing up and down and are maintained within the vertical plane by a set of weak hydrogen interactions [intra C - H⋯Cl and C - H⋯π(C≡CPh)] connecting the ortho-H of the phenyl rings with the chloride and acetylenic moieties, respectively. Complexes 1 and 2 react cleanly with phenylacetylene via dissociative loss of one alkynyphosphine ligand to yield saturated 18 e- Ru(II) vinylidene complexes [mer,cis-RuCl 2(C=CHPh)-(PPh2C≡CR)3] (R = Ph (12), Tol (13)). The catalytic activity of 1-4 in ROMP reactions of norbornene and several functionalized norbornenes in the presence of trimethylsilyldiazomethane (TMSD) as the carbene source is also described. © 2006 American Chemical Society.