Harnessing Multi‐Center‐2‐Electron Bonds for Carbene Metal‐Hydride Nanocluster Catalysis

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 (mc-ne) bonds to access a highly stable cyclic(alkyl)amino carbene (CAAC) copper-hydride nanocluster, [(CAAC)<sub>6</sub>Cu<sub>14</sub>H<sub>12</sub>][OTf]<sub>2</sub> 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.

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Publication Details

Journal
Angewandte Chemie International Edition
Published
2025-01-16
DOI
https://doi.org/10.1002/anie.202419537
Citations
1
Primary Topic
Asymmetric Hydrogenation and Catalysis
Type
article
Field-Weighted Citation Impact
0.54
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article

Harnessing Multi‐Center‐2‐Electron Bonds for Carbene Metal‐Hydride Nanocluster Catalysis

Milan Gembický, Quentin Pessemesse, Keary M. Engle, Pierre‐Adrien Payard et al.
1 citations
Angewandte Chemie International Edition
Asymmetric Hydrogenation and Catalysis
0.54
article

Harnessing Multi‐Center‐2‐Electron Bonds for Carbene Metal‐Hydride Nanocluster Catalysis

Milan Gembický, Quentin Pessemesse, Keary M. Engle, Pierre‐Adrien Payard, Jan Lorkowski, Jesse L. Peltier, Rodolphe Jazzar, Anne K. Ravn, Skyler D. Mendozza, Elguja Gojiashvili, Sourav S. Bera
article en
1 citations

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 (mc-ne) bonds to access a highly stable cyclic(alkyl)amino carbene (CAAC) copper-hydride nanocluster, [(CAAC)<sub>6</sub>Cu<sub>14</sub>H<sub>12</sub>][OTf]<sub>2</sub> 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.

Angewandte Chemie International EditionVol. 64(9)
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)
Openalex Percentile: Top 40%
Asymmetric Hydrogenation and Catalysis
0.54
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