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Reactivity of titanium pyrazolates towards CO2, CS2 and N2O.

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Title: Reactivity of titanium pyrazolates towards CO2, CS2 and N2O.
Authors: Kracht, Felix1 (AUTHOR), Mayer, Sophie1 (AUTHOR), Maichle-Mössmer, Cäcilia1 (AUTHOR), Anwander, Reiner1 (AUTHOR)
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. 7/28/2025, Vol. 54 Issue 28, p10890-10897. 8p.
Subjects: Carbon dioxide, Pyrazolates, Chemical reactions, Thermal stability, Oxo compounds, Thermogravimetry, Deoxygenation
Abstract: The tetravalent titanium pyrazolate Ti(pzMe2)4 inserts two molecules of carbon dioxide instantly at ambient temperature and 1 bar heteroallene, forming the complex Ti(CO2·pzMe2)2(pzMe2)2 (pzMe2 = 3,5-dimethylpyrazolato). CO2 insertion is reversible as proven by thermogravimetric analysis (TGA). Solid Ti(CO2·pzMe2)2(pzMe2)2 exhibits an exceptionally high stability at ambient atmosphere but converts in solution over time via deoxygenation into the oxo-bridged species [Ti(CO2·pzMe2)2(pzMe2)]2(μ-O) and [Ti(μ-O)2(μ-pzMe2)4(Ti{CO2·pzMe2}{pzMe2})2]. Treatment of Ti(pzMe2)4 with CS2 results in a mono-insertion to Ti(CS2·pzMe2)(pzMe2)3, which is reversible at 110 °C. Applying similar conditions, trivalent Ti(pztBu2)3 inserts also two molecules of CO2 to afford Ti(CO2·pztBu2)2(pztBu2) displaying complete de-insertion at 70 °C. At elevated temperatures compound Ti(CO2·pztBu2)2(pztBu2) does neither display redox activity nor engages in a deoxygenation reaction. While tetravalent Ti(pzMe2)4 does not react with N2O under ambient conditions, trivalent Ti(pztBu2)3 converts into oxo-bridged [Ti(pztBu2)3]2(μ-O) via initial N2O insertion and subsequent fast release of N2. [ABSTRACT FROM AUTHOR]
Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry 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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  Data: Reactivity of titanium pyrazolates towards CO<subscript>2</subscript>, CS<subscript>2</subscript> and N<subscript>2</subscript>O.
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  Data: <searchLink fieldCode="AR" term="%22Kracht%2C+Felix%22">Kracht, Felix</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Mayer%2C+Sophie%22">Mayer, Sophie</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Maichle-Mössmer%2C+Cäcilia%22">Maichle-Mössmer, Cäcilia</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Anwander%2C+Reiner%22">Anwander, Reiner</searchLink><relatesTo>1</relatesTo> (AUTHOR)
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  Data: <searchLink fieldCode="JN" term="%22Dalton+Transactions%3A+An+International+Journal+of+Inorganic+Chemistry%22">Dalton Transactions: An International Journal of Inorganic Chemistry</searchLink>. 7/28/2025, Vol. 54 Issue 28, p10890-10897. 8p.
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  Data: <searchLink fieldCode="DE" term="%22Carbon+dioxide%22">Carbon dioxide</searchLink><br /><searchLink fieldCode="DE" term="%22Pyrazolates%22">Pyrazolates</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+reactions%22">Chemical reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Thermal+stability%22">Thermal stability</searchLink><br /><searchLink fieldCode="DE" term="%22Oxo+compounds%22">Oxo compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Thermogravimetry%22">Thermogravimetry</searchLink><br /><searchLink fieldCode="DE" term="%22Deoxygenation%22">Deoxygenation</searchLink>
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  Data: The tetravalent titanium pyrazolate Ti(pzMe2)4 inserts two molecules of carbon dioxide instantly at ambient temperature and 1 bar heteroallene, forming the complex Ti(CO2·pzMe2)2(pzMe2)2 (pzMe2 = 3,5-dimethylpyrazolato). CO2 insertion is reversible as proven by thermogravimetric analysis (TGA). Solid Ti(CO2·pzMe2)2(pzMe2)2 exhibits an exceptionally high stability at ambient atmosphere but converts in solution over time via deoxygenation into the oxo-bridged species [Ti(CO2·pzMe2)2(pzMe2)]2(μ-O) and [Ti(μ-O)2(μ-pzMe2)4(Ti{CO2·pzMe2}{pzMe2})2]. Treatment of Ti(pzMe2)4 with CS2 results in a mono-insertion to Ti(CS2·pzMe2)(pzMe2)3, which is reversible at 110 °C. Applying similar conditions, trivalent Ti(pztBu2)3 inserts also two molecules of CO2 to afford Ti(CO2·pztBu2)2(pztBu2) displaying complete de-insertion at 70 °C. At elevated temperatures compound Ti(CO2·pztBu2)2(pztBu2) does neither display redox activity nor engages in a deoxygenation reaction. While tetravalent Ti(pzMe2)4 does not react with N2O under ambient conditions, trivalent Ti(pztBu2)3 converts into oxo-bridged [Ti(pztBu2)3]2(μ-O) via initial N2O insertion and subsequent fast release of N2. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
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  Group: Ab
  Data: <i>Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry 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: 10.1039/d5dt00957j
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      – Code: eng
        Text: English
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      Pagination:
        PageCount: 8
        StartPage: 10890
    Subjects:
      – SubjectFull: Carbon dioxide
        Type: general
      – SubjectFull: Pyrazolates
        Type: general
      – SubjectFull: Chemical reactions
        Type: general
      – SubjectFull: Thermal stability
        Type: general
      – SubjectFull: Oxo compounds
        Type: general
      – SubjectFull: Thermogravimetry
        Type: general
      – SubjectFull: Deoxygenation
        Type: general
    Titles:
      – TitleFull: Reactivity of titanium pyrazolates towards CO2, CS2 and N2O.
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            NameFull: Kracht, Felix
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            NameFull: Mayer, Sophie
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            NameFull: Maichle-Mössmer, Cäcilia
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            NameFull: Anwander, Reiner
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            – D: 28
              M: 07
              Text: 7/28/2025
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              Y: 2025
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              Value: 54
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            – TitleFull: Dalton Transactions: An International Journal of Inorganic Chemistry
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