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Updated: Sep 23, 2026

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Heterogeneous Palladium(0) Catalysts for C(sp3)-H Activation and Coupling to Form Hindered C-C Bonds
Prakash Basnet1, Bangaru Bhaskararao1, Peter A Amadeo1
1Department of Chemistry, Roy and Diana Vagelos Laboratories, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
Abstract:
Herein we explore the mechanism of palladium catalyzed alkylation of tertiary carbon centers predisposed to form captodative radical intermediates. SEM analysis of the isolated material from the reaction supports a heterogeneous palladium as the active catalyst. The reaction can also be carried out with commercially available Pd/C catalysts which feature a scope including previously failed substrates. A range of mechanism experiments and DFT calculations provide support for a catalytic cycle involving heterogeneous palladium. The potential of a favorable Pd(0) oxidative addition to a C-H bond vs a concerted metalation deprotonation from a more oxidized form of palladium is of particular interest. These discoveries provide the impetus to explore additional heterogeneous catalysts in C-H activation and to design of further effective substrates in these types of transformations.
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