View in EDS

Expanding the reactivity of Rosenthal's reagent to cyclopropenes and allenes.

Saved in:
Bibliographic Details
Title: Expanding the reactivity of Rosenthal's reagent to cyclopropenes and allenes.
Authors: Eilers, Marcel1 (AUTHOR), Geik, Dennis1 (AUTHOR), Schmidtmann, Marc1 (AUTHOR), Doye, Sven1 (AUTHOR), Beckhaus, Rüdiger1 (AUTHOR) ruediger.beckhaus@uni-oldenburg.de
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. 3/31/2026, Vol. 55 Issue 13, p5151-5160. 10p.
Subjects: Cyclopropene, Allene, Metal carbenes, Chemical reactions, X-ray diffraction, Ring formation (Chemistry), Nuclear magnetic resonance spectroscopy
Abstract: The reactions of the Rosenthal reagent Cp2Ti(η2-BTMSA) with cyclopropenes and allenes were systematically investigated. With cyclopropenes, selective 1,2-insertion into the Ti–C bond induces a ring expansion from three- to five-membered frameworks, affording titanacyclopentenes. These bicyclic complexes undergo rearrangement under mild conditions to generate highly reactive titanium carbene species, which subsequently participate in [2 + 2] cycloaddition reactions with alkynes (BTMSA and 1,2-diphenylacetylene), yielding titanacyclobutenes. In contrast, reactions with allenes proceed via ligand exchange of the alkyne ligand, giving titanacyclopentane derivatives. In addition to these transformations, the titanium complex was found to catalyze the isomerization of cyclotrideca-1,2-diene to cyclotrideca-1,3-diene. All isolated complexes were comprehensively characterized by NMR spectroscopy, and the solid-state structures of most species were identified by single-crystal X-ray diffraction. [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.)
Database: Engineering Source
FullText Text:
  Availability: 0
Header DbId: egs
DbLabel: Engineering Source
An: 192633852
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
PreciseRelevancyScore: 0
IllustrationInfo
Items – Name: Title
  Label: Title
  Group: Ti
  Data: Expanding the reactivity of Rosenthal's reagent to cyclopropenes and allenes.
– Name: Author
  Label: Authors
  Group: Au
  Data: <searchLink fieldCode="AR" term="%22Eilers%2C+Marcel%22">Eilers, Marcel</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Geik%2C+Dennis%22">Geik, Dennis</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Schmidtmann%2C+Marc%22">Schmidtmann, Marc</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Doye%2C+Sven%22">Doye, Sven</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Beckhaus%2C+Rüdiger%22">Beckhaus, Rüdiger</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> ruediger.beckhaus@uni-oldenburg.de</i>
– Name: TitleSource
  Label: Source
  Group: Src
  Data: <searchLink fieldCode="JN" term="%22Dalton+Transactions%3A+An+International+Journal+of+Inorganic+Chemistry%22">Dalton Transactions: An International Journal of Inorganic Chemistry</searchLink>. 3/31/2026, Vol. 55 Issue 13, p5151-5160. 10p.
– Name: Subject
  Label: Subjects
  Group: Su
  Data: <searchLink fieldCode="DE" term="%22Cyclopropene%22">Cyclopropene</searchLink><br /><searchLink fieldCode="DE" term="%22Allene%22">Allene</searchLink><br /><searchLink fieldCode="DE" term="%22Metal+carbenes%22">Metal carbenes</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+reactions%22">Chemical reactions</searchLink><br /><searchLink fieldCode="DE" term="%22X-ray+diffraction%22">X-ray diffraction</searchLink><br /><searchLink fieldCode="DE" term="%22Ring+formation+%28Chemistry%29%22">Ring formation (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Nuclear+magnetic+resonance+spectroscopy%22">Nuclear magnetic resonance spectroscopy</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: The reactions of the Rosenthal reagent Cp2Ti(η2-BTMSA) with cyclopropenes and allenes were systematically investigated. With cyclopropenes, selective 1,2-insertion into the Ti–C bond induces a ring expansion from three- to five-membered frameworks, affording titanacyclopentenes. These bicyclic complexes undergo rearrangement under mild conditions to generate highly reactive titanium carbene species, which subsequently participate in [2 + 2] cycloaddition reactions with alkynes (BTMSA and 1,2-diphenylacetylene), yielding titanacyclobutenes. In contrast, reactions with allenes proceed via ligand exchange of the alkyne ligand, giving titanacyclopentane derivatives. In addition to these transformations, the titanium complex was found to catalyze the isomerization of cyclotrideca-1,2-diene to cyclotrideca-1,3-diene. All isolated complexes were comprehensively characterized by NMR spectroscopy, and the solid-state structures of most species were identified by single-crystal X-ray diffraction. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  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.)
PLink https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=egs&AN=192633852
RecordInfo BibRecord:
  BibEntity:
    Identifiers:
      – Type: doi
        Value: 10.1039/d6dt00059b
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 10
        StartPage: 5151
    Subjects:
      – SubjectFull: Cyclopropene
        Type: general
      – SubjectFull: Allene
        Type: general
      – SubjectFull: Metal carbenes
        Type: general
      – SubjectFull: Chemical reactions
        Type: general
      – SubjectFull: X-ray diffraction
        Type: general
      – SubjectFull: Ring formation (Chemistry)
        Type: general
      – SubjectFull: Nuclear magnetic resonance spectroscopy
        Type: general
    Titles:
      – TitleFull: Expanding the reactivity of Rosenthal's reagent to cyclopropenes and allenes.
        Type: main
  BibRelationships:
    HasContributorRelationships:
      – PersonEntity:
          Name:
            NameFull: Eilers, Marcel
      – PersonEntity:
          Name:
            NameFull: Geik, Dennis
      – PersonEntity:
          Name:
            NameFull: Schmidtmann, Marc
      – PersonEntity:
          Name:
            NameFull: Doye, Sven
      – PersonEntity:
          Name:
            NameFull: Beckhaus, Rüdiger
    IsPartOfRelationships:
      – BibEntity:
          Dates:
            – D: 31
              M: 03
              Text: 3/31/2026
              Type: published
              Y: 2026
          Identifiers:
            – Type: issn-print
              Value: 14779226
          Numbering:
            – Type: volume
              Value: 55
            – Type: issue
              Value: 13
          Titles:
            – TitleFull: Dalton Transactions: An International Journal of Inorganic Chemistry
              Type: main
ResultId 1