Journal
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
Volume 14, Issue -, Pages 1537-1545Publisher
BEILSTEIN-INSTITUT
DOI: 10.3762/bjoc.14.130
Keywords
catalysis; C-H activation; density functional theory; London dispersion; reaction mechanisms
Categories
Funding
- Fonds der chemischen Industrie
- DFG [SPP 1807]
- University of Cologne within excellence initiative
Ask authors/readers for more resources
Carboxylate-assisted cobalt(III)-catalyzed C-H cyanations are highly efficient processes for the synthesis of (hetero) aromatic nitriles. We have now analyzed the cyanation of differently substituted 2-phenylpyridines in detail computationally by density functional theory and also experimentally. Based on our investigations, we propose a plausible reaction mechanism for this transformation that is in line with the experimental observations. Additional calculations, including NCIPLOT, dispersion interaction densities, and local energy decomposition analysis, for the model cyanation of 2-phenylpyridine furthermore highlight that London dispersion is an important factor that enables this challenging C-H transformation. Nonbonding interactions between the Cp* ligand and aromatic and C-H-rich fragments of other ligands at the cobalt center significantly contribute to a stabilization of cobalt intermediates and transition states.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available