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Solé-Daura AAuthorCarbó JjAuthorPoblet JmAuthor

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May 31, 2020
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Catalyst Design for Alkene Epoxidation by Molecular Analogues of Heterogeneous Titanium-Silicalite Catalysts

Publicated to:Acs Catalysis. 10 (8): 4737-4750 - 2020-04-17 10(8), DOI: 10.1021/acscatal.9b05147

Authors: Sole-Daura, Albert; Zhang, Teng; Fouilloux, Hugo; Robert, Carine; Thomas, Christophe M; Chamoreau, Lise-Marie; Carbo, Jorge J; Proust, Anna; Guillemot, Geoffroy; Poblet, Josep M

Affiliations

Institut de Recherche de Chimie Paris - Author
PSL Univ, CNRS, Chim ParisTech, Inst Rech Chim Paris, F-75005 Paris, France - Author
Sorbonne Univ, CNRS, Inst Parisien Chim Mol, F-75005 Paris, France - Author
Sorbonne Universite - Author
Univ Rovira & Virgili, Dept Quim Fis & Inorgan, Tarragona 43007, Spain - Author
Universitat Rovira i Virgili - Author
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Abstract

© 2020 American Chemical Society. The epoxidation of allylic alcohols with H2O2 catalyzed by the hybrid [α-B-SbW9O33(tBuSiO)3Ti(OiPr)]3- (1) anion as a molecular model of heterogeneous Ti-silicalite TS-1 catalyst was analyzed by means of DFT to determine the main factors that control the catalytic process and, finally, to improve the value of the available catalysts. Our calculations revealed that unlike other alkenes, allylic alcohols can bind the Ti center after activation of the precatalyst via hydrolysis to give the corresponding Ti-alcoholate, which is the catalyst resting state. Next, the dissociative addition of hydrogen peroxide to Ti causes the cleavage of a Ti-OSi junction to form a Ti(η2-OOH) moiety. The partial detachment of the Ti from the catalyst structure yields an intermediate with a flexible Ti center from which the Ti-OOH group can transfer an electrophilic oxygen to the alkene substrate in an inner-sphere fashion. The rate-determining process, which involves the heterolytic activation of H2O2 over the Ti(IV) and the electrophilic O-transfer, accounts for an overall free-energy barrier of 23.0 kcal mol-1 for 2-methyl-2-buten-1-ol, in line with the experimental value of 22.3. Conversely, the outer-sphere O-transfer - also accessible to nonfunctionalized alkenes - occurs through a more strained transition state that lays above in energy (by ∼4 kcal mol-1), giving a clue to explain the low yields reported experimentally for nonfunctionalized olefins. We also found that reducing the bulkiness of the substituents in the silanol functions of the catalyst has a positive influence on the catalytic activity, decreasing the overall free-energy barriers for the outer-sphere path. With this knowledge, we developed other catalytic species with tailored steric properties based on [SbW9O33(RSiOH)3]3- structure (R =iPr and nPr), which were synthesized, characterized, and successfully applied to the catalytic epoxidation of unfunctionalized alkenes. Present results clearly show that the detailed knowledge of the reaction mechanisms, even for complex processes, is possible nowadays and that the acquired information allows designing catalysts with desired activities.

Keywords

Active-sitesAsymmetric hydroformylationCatalyst designDftEpoxidationHydrogen-peroxideHydroperoxo complexesMechanistic studyOlefin epoxidationOxygen-transferPolyoxotungstatePropylene epoxidationSelective oxidationSilanolSilanol-functionalized polyoxotungstatesThioether oxidationTitanium

Quality index

Bibliometric impact. Analysis of the contribution and dissemination channel

The work has been published in the journal Acs Catalysis due to its progression and the good impact it has achieved in recent years, according to the agency WoS (JCR), it has become a reference in its field. In the year of publication of the work, 2020, it was in position 15/162, thus managing to position itself as a Q1 (Primer Cuartil), in the category Chemistry, Physical. Notably, the journal is positioned above the 90th percentile.

From a relative perspective, and based on the normalized impact indicator calculated from World Citations provided by WoS (ESI, Clarivate), it yields a value for the citation normalization relative to the expected citation rate of: 1.53. This indicates that, compared to works in the same discipline and in the same year of publication, it ranks as a work cited above average. (source consulted: ESI Nov 14, 2024)

This information is reinforced by other indicators of the same type, which, although dynamic over time and dependent on the set of average global citations at the time of their calculation, consistently position the work at some point among the top 50% most cited in its field:

  • Weighted Average of Normalized Impact by the Scopus agency: 1.55 (source consulted: FECYT Feb 2024)
  • Field Citation Ratio (FCR) from Dimensions: 7.13 (source consulted: Dimensions Aug 2025)

Specifically, and according to different indexing agencies, this work has accumulated citations as of 2025-08-02, the following number of citations:

  • WoS: 50
  • Scopus: 57
  • Google Scholar: 45

Impact and social visibility

From the perspective of influence or social adoption, and based on metrics associated with mentions and interactions provided by agencies specializing in calculating the so-called "Alternative or Social Metrics," we can highlight as of 2025-08-02:

  • The use, from an academic perspective evidenced by the Altmetric agency indicator referring to aggregations made by the personal bibliographic manager Mendeley, gives us a total of: 24.
  • The use of this contribution in bookmarks, code forks, additions to favorite lists for recurrent reading, as well as general views, indicates that someone is using the publication as a basis for their current work. This may be a notable indicator of future more formal and academic citations. This claim is supported by the result of the "Capture" indicator, which yields a total of: 24 (PlumX).

With a more dissemination-oriented intent and targeting more general audiences, we can observe other more global scores such as:

  • The Total Score from Altmetric: 5.35.
  • The number of mentions on the social network X (formerly Twitter): 9 (Altmetric).

Leadership analysis of institutional authors

This work has been carried out with international collaboration, specifically with researchers from: France.

There is a significant leadership presence as some of the institution’s authors appear as the first or last signer, detailed as follows: First Author (Solé Daura, Albert) and Last Author (Poblet Rius, Josep Maria).