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

22 August 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

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 leveraging 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. Using electrochemical measurements and thermogravimetric analysis we showcase that this cluster exhibits 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 a highly efficient and selective copper–hydride pre-catalyst across six reaction classes, thereby providing a bench-stable alternative for catalytic applications.

Keywords

N-heterocyclic carbenes
NHCs
copper hydride nanocluster
CuH catalysis
Quantum chemistry
Stryker’s reagent

Supplementary materials

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Description
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Supporting Info
Description
Experimental procedures, spectroscopic and crystallographic data, computational details and NMR spectra.
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