Aluminacyclopropene–phosphine complex: a carbene-exchange reagent
N-heterocyclic carbenes (NHCs) are extensively used as auxiliary ligands or organocatalysts thanks to their remarkable stability. However, due to their high structural stability, applications involving skeletal modifications without losing the low-valent nature (carbene exchange reactions) remain extremely rare. We report here that aluminacyclopropene-phosphine complex 1 promotes original "carbene-to-carbene" transformations of stable carbenes. Indeed, the Al(iii)-phosphine Lewis pair complex 1, due to its high ring strain, is able to react with NHC 2 to produce a cyclopropenylidene (4), <i>via</i> atomic carbon transfer from the NHC to the η<sup>2</sup>-coordinated alkyne fragment, within the coordination sphere of the Al(iii) center. Moreover, the complex 1 transforms the stable (diamino)cyclopropenylidene 7 into a more reactive acyclic (amino)carbene 8, which has been isolated in crystalline form.
Authors
- Huihui Xu (ORCID: https://orcid.org/0000-0002-4963-3437)
- José Miguel León Baeza
- Tsuyoshi Kato (ORCID: https://orcid.org/0000-0001-9003-4455)
- René S. Rojas (ORCID: https://orcid.org/0000-0002-5292-0816)
- Vicenç Branchadell (ORCID: https://orcid.org/0000-0003-3480-1669)
- Antoine Baceiredo (ORCID: https://orcid.org/0000-0002-6428-9697)
- Nathalie Saffon‐Merceron
Institutions
- Universitat Autònoma de Barcelona (ES)
- Centre National de la Recherche Scientifique (FR)
- Pontificia Universidad Católica de Chile (CL)
- Institut National Polytechnique de Toulouse (FR)
- Laboratoire de Chimie de Coordination (FR)
- Laboratoire Hétérochimie Fondamentale et Appliquée (FR)
Publication Details
- Journal
- Chemical Science
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d5sc03846d
- Citations
- 1
- Primary Topic
- Asymmetric Hydrogenation and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.54
Funders
- Agence Nationale de la Recherche
- Centre National de la Recherche Scientifique
- Agencia Nacional de Investigación y Desarrollo
- California State University, Chico
- Agencia Estatal de Investigación