English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

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

MPS-Authors
There are no MPG-Authors in the publication available
External Resource
No external resources are shared
Fulltext (restricted access)
There are currently no full texts shared for your IP range.
Fulltext (public)
There are no public fulltexts stored in PuRe
Supplementary Material (public)
There is no public supplementary material available
Citation

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)][BAr4F] (depe = 1,2-bis(diethylphosphino)ethane; BAr4F = 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.