Harnessing Multi‐Center‐2‐Electron Bonds for Carbene Metal‐Hydride Nanocluster Catalysis
Abstract N ‐Heterocyclic carbene (NHC) ligands possess the ability to stabilize metal‐based nanomaterials for a broad range of applications. With respect to metal‐hydride nanomaterials, however, carbenes are rare, which is surprising if one considers the importance of metal‐hydride bonds across the chemical sciences. In this study, we introduce a bottom‐up approach that leverages preexisting metal‐metal m‐center‐n‐electron ( m c‐ n e) bonds to access a highly stable cyclic(alkyl)amino carbene (CAAC) copper‐hydride nanocluster, [(CAAC) 6 Cu 14 H 12 ][OTf] 2 with superior stability compared to Stryker's reagent, a popular commercial phosphine‐based copper hydride catalyst. Density functional theory (DFT) calculations reveal that the enhanced stability stems from hydride‐to‐ligand backbonding with the π‐accepting carbene. This new cluster emerges as an efficient and selective copper‐hydride pre‐catalyst, thereby providing a bench‐stable alternative for catalytic applications.
Authors
- Milan Gembický (ORCID: https://orcid.org/0000-0002-3898-1612)
- Quentin Pessemesse (ORCID: https://orcid.org/0000-0002-3801-792X)
- Keary M. Engle (ORCID: https://orcid.org/0000-0003-2767-6556)
- Pierre‐Adrien Payard (ORCID: https://orcid.org/0000-0001-5661-6128)
- Jan Lorkowski (ORCID: https://orcid.org/0000-0003-3436-1296)
- Jesse L. Peltier (ORCID: https://orcid.org/0000-0002-3493-2127)
- Rodolphe Jazzar (ORCID: https://orcid.org/0000-0002-4156-7826)
- Anne K. Ravn (ORCID: https://orcid.org/0000-0002-7040-3230)
- Skyler D. Mendozza
- Elguja Gojiashvili (ORCID: https://orcid.org/0000-0002-1810-8947)
- Sourav S. Bera
Institutions
- Université Claude Bernard Lyon 1 (FR)
- Scripps Research Institute (US)
- Northeastern University (US)
- Centre National de la Recherche Scientifique (FR)
- San Diego State University (US)
- University of California San Diego (US)
- Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (FR)
- North Eastern University (TH)
- Institut National des Sciences Appliquées de Lyon (FR)
Publication Details
- Journal
- Angewandte Chemie
- Published
- 2025-01-16
- DOI
- https://doi.org/10.1002/ange.202419537
- Citations
- 1
- Primary Topic
- Asymmetric Hydrogenation and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.54
Funders
- National Science Foundation
- San Diego State University
- Agence Nationale de la Recherche
- Grand Équipement National De Calcul Intensif
- University of California, San Diego
- Division of Chemistry