C–H Activation by Isolable Cationic Bis(phosphine) Cobalt(III) Metallacycles

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

doi:10.1021/jacs.2c08865

Item

ITEM ACTIONSEXPORT

Add to Basket

Local TagsRelease HistoryDetailsSummary

Released

Journal Article

C–H Activation by Isolable Cationic Bis(phosphine) Cobalt(III) Metallacycles

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)

jacs.2c08865-accepted-Pure.pdf
(Postprint), 2MB

Supplementary Material (public)

There is no public supplementary material available

Citation

Whitehurst, W. G., Kim, J., Koenig, S. G., & Chirik, P. J. (2022). C–H Activation by Isolable Cationic Bis(phosphine) Cobalt(III) Metallacycles. Journal of the American Chemical Society, 144(41), 19186-19195. doi:10.1021/jacs.2c08865.

Cite as: https://hdl.handle.net/21.11116/0000-000D-3C2B-1

Abstract

Five- and six-coordinate cationic bis(phosphine) cobalt(III) metallacycle complexes were synthesized with the general structures, [(depe)Co(cycloneophyl)(L)(L′)][BAr^F₄] (depe = 1,2-bis(diethylphosphino)ethane; cycloneophyl = [κ-C:C-(CH₂C(Me)₂)C₆H₄]; L/L′ = pyridine, pivalonitrile, or the vacant site, BAr₄^F = B[(3,5-(CF₃)₂)C₆H₃]₄). Each of these compounds promoted facile directed C(sp²)–H activation with exclusive selectivity for ortho-alkylated products, consistent with the selectivity of reported cobalt-catalyzed arene-alkene-alkyne coupling reactions. The direct observation of C–H activation by cobalt(III) metallacycles provided experimental support for the intermediacy of these compounds in this class of catalytic C–H functionalization reaction. Deuterium labeling and kinetic studies provided insight into the nature of C–H bond cleavage and C–C bond reductive elimination from isolable cobalt(III) precursors.