Harnessing Multi-Center-2-Electron Bonds for Carbene Metal-Hydride Nanocluster Catalysis
Quentin Pessemesse1, Skyler D Mendoza2, Jesse L Peltier3,4
1Univ Lyon, INSA Lyon, Université Lyon 1, CNRS, CPE Lyon, UMR 5246, ICBMS., 1 rue Victor Grignard, Villeurbanne Cedex, France.
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)6Cu14H12][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.
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