Outer-Sphere Control of Catalysis on Surfaces: A Comparative Study of Ti(IV) Single-Sites Grafted on Amorphous versus Crystalline Silicates for Alkene Epoxidation.

The effect of outer-sphere environment on alkene epoxidation catalysis using an organic hydroperoxide oxidant is demonstrated for calix[4]arene-Ti single-sites grafted on amorphous vs crystalline delaminated zeotype (UCB-4) silicates as supports. A chelating calix[4]arene macrocyclic ligand helps en...

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Published in:Journal of the American Chemical Society Vol. 140; no. 15; pp. 4956 - 4961
Main Authors: Grosso-Giordano, Nicolás A., Schroeder, Christian, Okrut, Alexander, Solovyov, Andrew, Schhöttle, Christian, Chassé, Walter, Marinkovic, Nebojša, Koller, Hubert, Zones, Stacey I., Katz, Alexander
Format: Article
Published: American Chemical Society 4/18/2018
Subjects:
Online Access:View this record in EBSCOhost
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      dt: 4/18/2018
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        atl: Outer-Sphere Control of Catalysis on Surfaces: A Comparative Study of Ti(IV) Single-Sites Grafted on Amorphous versus Crystalline Silicates for Alkene Epoxidation.
      aug:
        au:
          Grosso-Giordano, Nicolás A.
          Schroeder, Christian
          Okrut, Alexander
          Solovyov, Andrew
          Schhöttle, Christian
          Chassé, Walter
          Marinkovic, Nebojša
          Koller, Hubert
          Zones, Stacey I.
          Katz, Alexander
        affil:
          Department of Chemical and Biomolecular Engineering, University of California, Berkeley, Berkeley, California 94720, United States
          Institut für Physikalische Chemie, Westfälische Wilhelms-Universität Münster, Münster 48149, Germany
          Department of Chemical Engineering, Columbia University, New York, New York 10027, United States
          Chevron Energy Technology Company, Richmond, California 94804, United States
      su:
        Catalysis
        Comparative studies
        Amorphous substances
        Silicates
        Alkenes
      sug:
        subj:
          Catalysis
          Comparative studies
          Amorphous substances
          Silicates
          Alkenes
      ab: The effect of outer-sphere environment on alkene epoxidation catalysis using an organic hydroperoxide oxidant is demonstrated for calix[4]arene-Ti single-sites grafted on amorphous vs crystalline delaminated zeotype (UCB-4) silicates as supports. A chelating calix[4]arene macrocyclic ligand helps enforce a constant Ti inner-sphere, as characterized by UV-visible and X-ray absorption spectroscopies, thus enabling the rigorous comparison of outer-sphere environments across different siliceous supports. These outer-sphere environments are characterized by solid-state ¹H NMR spectroscopy to comprise proximally organized silanols confined within 12 membered-ring cups in crystalline UCB-4, and are responsible for up to 5-fold enhancements in rates of epoxidation by Ti centers.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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