Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane.

Two compatible organometallic complexes, W(Me) (1) and TiNp (2), were successively anchored on a highly dehydroxylated single silica support (SiO) to synthesize the well-defined bimetallic precatalyst [(?Si-O-)W(Me)(?Si-O-)Ti(Np)] (4). Precatalyst 4 was characterized at the molecular level using adv...

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Publicado en:Journal of the American Chemical Society Vol. 139; no. 9; pp. 3522 - 3528
Autores principales: Samantaray, Manoja K., Kavitake, Santosh, Morlanés, Natalia, Abou-Hamad, Edy, Hamieh, Ali, Dey, Raju, Basset, Jean-Marie
Formato: Resumen
Publicado: American Chemical Society 3/8/2017
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Acceso en línea:Ver este registro en EBSCOhost
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        10.1021/jacs.6b12970
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        atl: Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane.
      aug:
        au:
          Samantaray, Manoja K.
          Kavitake, Santosh
          Morlanés, Natalia
          Abou-Hamad, Edy
          Hamieh, Ali
          Dey, Raju
          Basset, Jean-Marie
        affil: King Abdullah University of Science and Technology, KAUST Catalysis Center (KCC), Thuwal 23955-6900, Saudi Arabia
      su:
        Metals
        Propane
        Silica
      sug:
        subj:
          Metals
          Propane
          Silica
      ab: Two compatible organometallic complexes, W(Me) (1) and TiNp (2), were successively anchored on a highly dehydroxylated single silica support (SiO) to synthesize the well-defined bimetallic precatalyst [(?Si-O-)W(Me)(?Si-O-)Ti(Np)] (4). Precatalyst 4 was characterized at the molecular level using advanced surface organometallic chemistry (SOMC) characterization techniques. The strong autocorrelation observed between methyl of W and Ti in H-H multiple-quantum NMR spectra demonstrates that W and Ti species are in close proximity to each other. The bimetallic precatalyst 4, with a turnover number (TON) of 9784, proved to be significantly more efficient than the silica-supported monometallic catalyst [(?Si-O-)W(Me)] (3), with a TON of 98, for propane metathesis at 150 °C in a flow reactor. The dramatic improvement in the activity signifies the cooperativity between Ti and W and indicates that the key step of alkane metathesis (C-H bond activation followed by β-H elimination) occurs on Ti, followed by olefin metathesis, which occurs on W. We have demonstrated the influence and importance of proximity of Ti to W for achieving such a significantly high activity. This is the first report demonstrating the considerably high activity (TON = 9784) in propane metathesis at moderate temperature (150 °C) using a well-defined bimetallic system prepared via the SOMC approach.
      pubtype: Academic Journal
      doctype: Abstract
      src: R
    language: English
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