Given the interesting scenario of two possible ligand coordination modes (via O,N-and N,N-) by the urea ligand, DFT calculations for the given solvent mixture (1:3:1) were performed at the PW6B95-D4/def2-TZVPP+SMD(n-PrOAc/n-heptane/TFE// TPSS-D3(BJ)/def2-SVP level of theory, investigating both the pathways towards major and minor regioisomers (Scheme 5E). Here, the standard benzamide 1 and 1-alkynyl indole 2 were chosen to model the elementary steps: alkyne coordination, migratory insertion, and reductive elimination (see Supporting Information for details). The calculations suggested the migratory insertion as the rate determining step where the O,N-coordination mode was energetically more favorable over the N,N-coordination, even with prominent agostic interaction between cobalt(III) and hydrogen atom in the later cobaltacycle (Int-2). Moreover, the O,N-coordinating state pathway was favorable over N,N-coordinating state pathway towards accessing both major (ΔΔG ‡ mono = 19.5 kcal mol -1 ) as well as minor (ΔΔG ‡ dual = 21.1 kcal mol -1 ) regioisomeric intermediates Int-4A and Int-4B, respectively. Moreover, the mono atropoisomer pathway proved to be favored over the dual atropoisomer by ΔΔG ‡ = 3.4 kcal mol -1 (TS-1), which is in agreement with the experiments.