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Updated: Jun 12, 2025

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Metal-Carbon Bond Heterolysis Energy Scale for Model Palladium Catalysts
Bin-Rui Mo1, Jun-Yan Wu1, Jin-Dong Yang1
1Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing 100084, China.
Abstract:
Thermodynamic studies of transition-metal intermediates are crucial for understanding of metal-catalyzed transformations. Herein, a series of arylpalladium cyanomethanides were synthesized and characterized. Their palladium-carbon bond heterolysis energies (ΔGhet(Pd-C)) were determined in DMSO for the first time by equilibrium methods. ΔGhet(Pd-C) values of 7.9-19.1 kcal/mol, located between the ΔGhet(Pd-O) and ΔGhet(Pd-N) scales previously established, are much smaller than the corresponding ΔGhet(C-H)s of phenylacetonitrile (30.0 kcal/mol). Linear free energy relationship (LEFR) analysis reveals insights into the structure-property relationship and the factor dictating the thermodynamics of metalation. These ΔGhet(Pd-X)s in combination with ΔGhet(X-H)s are successfully used to diagnose the reaction feasibility and selectivity of X-H bond activation.
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