C(sp3)–C(sp2) Reductive Elimination versus β-Hydride Elimination from 
Cobalt(III) Intermediates in Catalytic C–H Functionalization

Whitehurst, William G.; Kim, Junho; Koenig, Stefan G.; Chirik, Paul J.

doi:10.1021/acscatal.3c01874

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C(sp³)–C(sp²) Reductive Elimination versus β-Hydride Elimination from Cobalt(III) Intermediates in Catalytic C–H Functionalization

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Whitehurst, W. G., Kim, J., Koenig, S. G., & Chirik, P. J. (2023). C(sp³)–C(sp²) Reductive Elimination versus β-Hydride Elimination from Cobalt(III) Intermediates in Catalytic C–H Functionalization. ACS Catalysis, 13(13), 8700-8707. doi:10.1021/acscatal.3c01874.

Cite as: https://hdl.handle.net/21.11116/0000-000F-4B07-6

Abstract

The cationic bis(phosphine) cobalt(I) arene complex, [(depe)Co(η⁶-C₇H₈)][BAr₄^F] (depe = 1,2-bis(diethylphosphino)ethane; BAr₄^F = B[(3,5-(CF₃)₂)C₆H₃]₄), was investigated as a precatalyst for three-component coupling of arenes, alkenes, and alkynes. Although a sterically attenuated catalyst was targeted with the goal of accelerating C–H functionalization, hydrovinylation derived from the alkene and alkyne was favored over three-component coupling. Remarkably, no catalytic hydrovinylation was observed in the absence of arene, demonstrating the role of C–H activation in the hydrovinylation process and ruling out a mechanism that involves β-H elimination from a cobalt(III) metallacycle. Deuterium labeling supported β-H elimination from a putative cobalt(III)–alkyl,aryl intermediate that forms after C–H activation by a cobalt(III) metallacycle. By varying the arene and alkene coupling partners, factors affecting the selectivity of C(sp³)–C(sp²) reductive elimination versus β-H elimination from the cobalt(III)–alkyl,aryl intermediate were determined.