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Epoxidation at Isolated Titanium Site Modeled by Ti‐Siloxy‐Polyoxometalates Built on [α–A–XW9O34]n− and [α–B–YW9O33]9−: Comparative Study of Their Hydrolytic Stability

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Title: Epoxidation at Isolated Titanium Site Modeled by Ti‐Siloxy‐Polyoxometalates Built on [α–A–XW9O34]n− and [α–B–YW9O33]9−: Comparative Study of Their Hydrolytic Stability
Authors: K/Bidi, Ludivine1 (AUTHOR), Solé‐Daura, Albert2 (AUTHOR), Zhang, Teng1 (AUTHOR), Desjonquères, Alix1 (AUTHOR), Poblet, Josep M.2 (AUTHOR), Proust, Anna1 (AUTHOR), Carbó, Jorge J.2 (AUTHOR) j.carbo@urv.cat, Guillemot, Geoffroy1 (AUTHOR) geoffroy.guillemot@sorbonne-universite.fr
Source: ChemCatChem. 1/9/2025, Vol. 17 Issue 1, p1-9. 9p.
Subjects: Titanium silicate, Hydrogen peroxide, Nuclear magnetic resonance spectroscopy, Catalytic activity, Epoxidation
Abstract: This report investigates the structural differences in a series of titanium complexes constructed from silanol functionalized polyoxometalate (SiloxPOMs) derivatives, designed to create a constrained coordination site for titanium (IV) cations, namely (THA)3[PW9O34(tBuSiO)3Ti(OiPr)] and (THA)3[SbW9O33(tBuSiO)3Ti(OiPr)]. The complexes serve as structural and functional models for titanium silicates, facilitating the epoxidation of allylic alcohols and alkenes by aqueous hydrogen peroxide solutions. The different activity and selectivity observed between the two derivatives are attributed to variations in the polyoxotungstic platform used, A‐type–[XW9O34]n− versus B‐type –[YW9O33]3−. A combined experimental and theoretical investigation highlights the influence of these structural differences on water interaction and hydrolytic stability, with A‐type structures proving more susceptible to hydrolysis. In addition, the study also delves into the nuclearity of the active sites, a monomeric titanium (IV)‐hydroperoxide [Ti]–(OOH) active species evidenced by diffusion NMR spectroscopy, and the influence of the presence of water on catalytic performance in epoxidation reaction, thus shedding light on the relationship between catalyst stability, intermediates formed and reaction pathway. The study finally demonstrates the suitability of B‐type SiloxPOM derivatives as models for titanium silicates, offering insights into their stability and catalytic activity for epoxidation reactions. [ABSTRACT FROM AUTHOR]
Copyright of ChemCatChem is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Label: Title
  Group: Ti
  Data: Epoxidation at Isolated Titanium Site Modeled by Ti‐Siloxy‐Polyoxometalates Built on [α–A–XW<subscript>9</subscript>O<subscript>34</subscript>]<superscript>n</superscript><superscript>−</superscript> and [α–B–YW<subscript>9</subscript>O<subscript>33</subscript>]<superscript>9−</superscript>: Comparative Study of Their Hydrolytic Stability
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  Data: <searchLink fieldCode="AR" term="%22K%2FBidi%2C+Ludivine%22">K/Bidi, Ludivine</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Solé‐Daura%2C+Albert%22">Solé‐Daura, Albert</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Zhang%2C+Teng%22">Zhang, Teng</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Desjonquères%2C+Alix%22">Desjonquères, Alix</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Poblet%2C+Josep+M%2E%22">Poblet, Josep M.</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Proust%2C+Anna%22">Proust, Anna</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Carbó%2C+Jorge+J%2E%22">Carbó, Jorge J.</searchLink><relatesTo>2</relatesTo> (AUTHOR)<i> j.carbo@urv.cat</i><br /><searchLink fieldCode="AR" term="%22Guillemot%2C+Geoffroy%22">Guillemot, Geoffroy</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> geoffroy.guillemot@sorbonne-universite.fr</i>
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  Data: <searchLink fieldCode="JN" term="%22ChemCatChem%22">ChemCatChem</searchLink>. 1/9/2025, Vol. 17 Issue 1, p1-9. 9p.
– Name: Subject
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  Data: <searchLink fieldCode="DE" term="%22Titanium+silicate%22">Titanium silicate</searchLink><br /><searchLink fieldCode="DE" term="%22Hydrogen+peroxide%22">Hydrogen peroxide</searchLink><br /><searchLink fieldCode="DE" term="%22Nuclear+magnetic+resonance+spectroscopy%22">Nuclear magnetic resonance spectroscopy</searchLink><br /><searchLink fieldCode="DE" term="%22Catalytic+activity%22">Catalytic activity</searchLink><br /><searchLink fieldCode="DE" term="%22Epoxidation%22">Epoxidation</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: This report investigates the structural differences in a series of titanium complexes constructed from silanol functionalized polyoxometalate (SiloxPOMs) derivatives, designed to create a constrained coordination site for titanium (IV) cations, namely (THA)3[PW9O34(tBuSiO)3Ti(OiPr)] and (THA)3[SbW9O33(tBuSiO)3Ti(OiPr)]. The complexes serve as structural and functional models for titanium silicates, facilitating the epoxidation of allylic alcohols and alkenes by aqueous hydrogen peroxide solutions. The different activity and selectivity observed between the two derivatives are attributed to variations in the polyoxotungstic platform used, A‐type–[XW9O34]n− versus B‐type –[YW9O33]3−. A combined experimental and theoretical investigation highlights the influence of these structural differences on water interaction and hydrolytic stability, with A‐type structures proving more susceptible to hydrolysis. In addition, the study also delves into the nuclearity of the active sites, a monomeric titanium (IV)‐hydroperoxide [Ti]–(OOH) active species evidenced by diffusion NMR spectroscopy, and the influence of the presence of water on catalytic performance in epoxidation reaction, thus shedding light on the relationship between catalyst stability, intermediates formed and reaction pathway. The study finally demonstrates the suitability of B‐type SiloxPOM derivatives as models for titanium silicates, offering insights into their stability and catalytic activity for epoxidation reactions. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of ChemCatChem is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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      – Type: doi
        Value: 10.1002/cctc.202401106
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      – Code: eng
        Text: English
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      Pagination:
        PageCount: 9
        StartPage: 1
    Subjects:
      – SubjectFull: Titanium silicate
        Type: general
      – SubjectFull: Hydrogen peroxide
        Type: general
      – SubjectFull: Nuclear magnetic resonance spectroscopy
        Type: general
      – SubjectFull: Catalytic activity
        Type: general
      – SubjectFull: Epoxidation
        Type: general
    Titles:
      – TitleFull: Epoxidation at Isolated Titanium Site Modeled by Ti‐Siloxy‐Polyoxometalates Built on [α–A–XW9O34]n− and [α–B–YW9O33]9−: Comparative Study of Their Hydrolytic Stability
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            – D: 09
              M: 01
              Text: 1/9/2025
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