TY - JOUR A1 - Detmar, Eric A1 - Müller, Valentin A1 - Zell, Daniel A1 - Ackermann, Lutz A1 - Breugst, Martin T1 - Cobalt-catalyzed C–H cyanations: Insights into the reaction mechanism and the role of London dispersion JF - Beilstein Journal of Organic Chemistry PY - 2018/// VL - 14 SP - 1537 EP - 1545 SN - 1860-5397 DO - 10.3762/bjoc.14.130 PB - Beilstein-Institut JA - Beilstein J. Org. Chem. UR - https://doi.org/10.3762/bjoc.14.130 KW - catalysis KW - C–H activation KW - density functional theory KW - London dispersion KW - reaction mechanisms N2 - 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. ER -