Metal–Carbon Bond Heterolysis Energy Scale for Model Palladium Catalysts
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 (Δ<i>G</i><sub>het</sub>(Pd-C)) were determined in DMSO for the first time by equilibrium methods. Δ<i>G</i><sub>het</sub>(Pd-C) values of 7.9-19.1 kcal/mol, located between the Δ<i>G</i><sub>het</sub>(Pd-O) and Δ<i>G</i><sub>het</sub>(Pd-N) scales previously established, are much smaller than the corresponding Δ<i>G</i><sub>het</sub>(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 Δ<i>G</i><sub>het</sub>(Pd-X)s in combination with Δ<i>G</i><sub>het</sub>(X-H)s are successfully used to diagnose the reaction feasibility and selectivity of X-H bond activation.
Authors
- Junyan Wu (ORCID: https://orcid.org/0000-0003-0870-382X)
- Bin-Rui Mo
- Jin‐Pei Cheng (ORCID: https://orcid.org/0000-0001-8822-1577)
- Jin‐Dong Yang (ORCID: https://orcid.org/0000-0001-7351-2152)
Institutions
- Nankai University (CN)
- Unité Matériaux et Transformations (FR)
- Tsinghua University (CN)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2024-09-27
- DOI
- https://doi.org/10.1021/acs.inorgchem.4c03225
- Citations
- 4
- Primary Topic
- Carbon dioxide utilization in catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.71
Funders
- National Natural Science Foundation of China