Mechanistic Interrogation of Alkyne Hydroarylations Catalyzed by Highly Reduced, Single-Component Cobalt Complexes

Highly reactive catalysts for <i>ortho</i>-hydroarylations of alkynes have previously been reported to result from activation of CoBr₂ by Grignard reagents, but the operative mechanism and identity of the active cobalt species have been undefined. A mechanistic analysis of a related system, involving hydroarylations of a (<i>N</i>-aryl)aryl ethanimine with diphenylacetylene, was performed using isolable reduced Co complexes. Studies of the stoichiometric reaction of Co(I) or Co(II) precursors with CyMgCl implicated catalyst initiation via a β-H elimination/deprotonation pathway. The resulting single-component Co(-I) complex is proposed as the direct pre-catalyst. Michaelis-Menten enzyme kinetic studies provide mechanistic details regarding the catalytic dependence on substrate. The (<i>N</i>-aryl)aryl ethanimine substrate exhibited saturation-like behavior, whereas alkyne demonstrated a complex dependency; rate inhibition and promotion depend on the relative concentration of alkyne to imine. Activation of the aryl C-H bond occurred only in the presence of coordinated alkyne, which suggests operation of a concerted metalation-deprotonation (CMD) mechanism. Small primary isotope effects are consistent with a rate-determining C-H cleavage. Off-cycle olefin isomerization catalyzed by the same Co(-I) active species appears to be responsible for the observed <i>Z</i>-selectivity.