Ruthenium(II) and Ruthenium(IV) Complexes Containing kappa1-P-, kappa2-P,O-, and kappa3-P,N,O Iminophosphorane- Phosphine Ligands Ph2PCH2P{=NP(=O)(OR)2}PH2 (R = Et, Ph): Synthesis, Reactivity, Theoretical Studies, and Catalytic Activity in Transfer Hydrogenation of Cyclohexanone

  1. Cadierno, V. 1
  2. Crochet, P. 1
  3. Díez, J. 1
  4. García-Álvarez, J. 1
  5. García-Garrido, S.E. 1
  6. Gimeno, J. 1
  7. García-Granda, S. 1
  8. Rodríguez, M.A. 2
  1. 1 Universidad de Oviedo
    info

    Universidad de Oviedo

    Oviedo, España

    ROR https://ror.org/006gksa02

  2. 2 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

Revista:
Inorganic Chemistry

ISSN: 0020-1669

Año de publicación: 2003

Volumen: 42

Número: 10

Páginas: 3293-3307

Tipo: Artículo

DOI: 10.1021/IC020702K SCOPUS: 2-s2.0-0038366760 WoS: WOS:000182962800020 GOOGLE SCHOLAR

Otras publicaciones en: Inorganic Chemistry

Repositorio institucional: lock_openAcceso abierto Editor

Resumen

[{Ru(η6-p-cymene)(μ-Cl)Cl}2] and [{Ru(η3:η3-C10H16) (μ-Cl)Cl}2] react with Ph2PCH2P{=NP(=O)(OR)2}Ph2 (R = Et (1a), Ph (1b)) affording complexes [Ru(η-p-cymene)Cl2Cl2(κ1-P- Ph2PCH2P{=NP(=O)(OR)2}Ph2)] (R = Et (2a), Ph (2b)) and [Ru(η3:η3-C10H16) Cl2(κ1-P-Ph2PCH2P{=NP(=O) (OR)2}Ph2)] (R = Et (6a), Ph (6b)). While treatment of 2a with 1 equiv of AgSbF6 yields a mixture of [Ru(η6-p-cymene)Cl(κ2-P, O-Ph2PCH2P{=NP(=O)(OEt)2}Ph2)]- [SbF6] (3a) and [Ru(η6-p-cymene)Cl(κ2-P,N-Ph2 PCH2P{=NP(=O)(OEt)2}Ph2)][SbF6] (4a), [Ru(η6-p-cymene)Cl(κ2. P,O-Ph2PCH2P{=NP(=O)(OPh)2} Ph2)][SbF6] (3b) and [Ru(η3:η3-C10H16)Cl (κ2-P,O-Ph2PCH2P{=NP(=O) (OR)2}-Ph2)][SbF6] (R = Et (7a), Ph (7b)) are selectively formed from 2b and 6a,b. Complexes [Ru(η6-p-cymene)(κ3-P,N,O-Ph2 PCH2P{=NP(=O)(OR)2}Ph2)] [SbF6]2 (R = Et (5a), Ph (5b)) and [Ru(η3:η3-C10H16) (κ3-P,N,O-Ph2PCH2P{= NP(=O)(OR)2}Ph2)][SbF6]2 (R = Et (8a), Ph (8b)) have been prepared using 2 equiv of AgSbF6. The reactivity of 3-5a,b has been explored allowing the synthesis of [Ru(η6-p-cymene)X2(κ1-P- Ph2PCH2P{=NP(=O)(OR)2}Ph2)] (R = Et, Ph; X = Br, I, N3, NCO (9-12a,b)). The catalytic activity of 2-8a,b in transfer hydrogenation of cyclohexanone, as well as theoretical calculations on the models [Ru(η6-C6H6)Cl(κ2-P, N-H2PCH2P{=NP(=O)-(OH)2} H2)]+ and [Ru(η6-C6H6)Cl(κ2-P, O-H2PCH2P{=NP(=O)(OH)2} H2)]+, has been also studied.