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Mechanistic Insights into Iron-Catalyzed C-H Bond Activation and C-C Coupling

Brewer, Samantha M.; Schwartz, Timothy M.; Mekhail, Magy A.; Turan, Lara S.; Prior, Timothy J.; Hubin, Timothy J.; Janesko, Benjamin G.; Green, Kayla N.

Authors

Samantha M. Brewer

Timothy M. Schwartz

Magy A. Mekhail

Lara S. Turan

Timothy J. Hubin

Benjamin G. Janesko

Kayla N. Green



Abstract

Iron-catalyzed C-C coupling reactions of pyrrole provide a unique alternative to the traditional Pd-catalyzed counterpart. However, many details regarding the actual mechanism remain unknown. A series of macrocyclic iron(III) complexes were used to evaluate specifics related to the role of O2, radicals, and μ-oxodiiron-complex participation in the catalytic cycle. It was determined that the mononuclear tetra-azamacrocyclic complex is a true catalyst and not a stoichiometric reagent, while more than one equivalent of a sacrificial oxidant is needed. Furthermore, the reaction does not proceed through an organic radical pathway. μ-Oxodiiron complexes are not involved in the main catalytic pathway, and the dimers are, in fact, off-cycle species that decrease catalytic efficiency.

Citation

Brewer, S. M., Schwartz, T. M., Mekhail, M. A., Turan, L. S., Prior, T. J., Hubin, T. J., …Green, K. N. (in press). Mechanistic Insights into Iron-Catalyzed C-H Bond Activation and C-C Coupling. Organometallics, https://doi.org/10.1021/acs.organomet.1c00211

Journal Article Type Article
Acceptance Date Jul 2, 2021
Online Publication Date Jul 20, 2021
Deposit Date Jul 22, 2021
Publicly Available Date Jul 21, 2022
Journal Organometallics
Print ISSN 0276-7333
Electronic ISSN 1520-6041
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
DOI https://doi.org/10.1021/acs.organomet.1c00211
Keywords Absorption; Ligands; Oligomers; Pyrroles; Oxygen
Public URL https://hull-repository.worktribe.com/output/3808910