Nitrene-Transfer Chemistry to Olefins Mediated by Co(III) Catalysts Supported by a Tetraamido Macrocycle.
- 1Department of Chemistry, Missouri University of Science and Technology, Rolla, Missouri65409, United States.
Abstract
A tetraamido macrocyclic ligand scaffold (L1H4) has been synthesized and metalated with Co(III) to afford anionic metal complexes [CoIII(L1)]- (cations: K+, PPh4+) that are paramagnetic (S = 1) in solution and display semi-reversible reduction waves (CoII/III) and irreversible anodic events in cyclic voltammograms. These macrocyclic Co(III) compounds have been examined as nitrene-transfer catalysts, involving iminoiodinane precursors (PhI=NR) and olefins, to reveal efficient aziridinations and/or allylic aminations, especially with sterically unencumbered styrenes. Mechanistic studies indicate that stepwise formation of two N-C bonds is operative in aziridinations, in which both polar and radical contributions are evident, in contrast to analogous nitrene-transfer chemistry displayed by [CoIII(TAMLred)]-, the latter relying on single-electron transfer between ligand and substrate. The generation of both mono- and bis-nitrene cobalt complexes or derivatives is indicated by ESI-MS, but their precise structural identity, electronic configuration, and relevance in nitrene-transfer chemistry remains an area for further exploration.
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BibTeX
@article{bhatia2026nitrenetransfer,
title = {{Nitrene-Transfer Chemistry to Olefins Mediated by Co(III) Catalysts Supported by a Tetraamido Macrocycle.}},
author = {Himanshu Bhatia and Jacob Green and Mia Ehrhart and Rohit G Jadhav and Amitava Choudhury and Pericles Stavropoulos},
journal = {Inorganic chemistry},
year = {2026},
month = oct,
doi = {10.1021/acs.inorgchem.6c02795},
url = {https://europepmc.org/article/MED/42831556},
note = {CC BY},
}
RIS
TY - JOUR
TI - Nitrene-Transfer Chemistry to Olefins Mediated by Co(III) Catalysts Supported by a Tetraamido Macrocycle.
AU - Himanshu Bhatia
AU - Jacob Green
AU - Mia Ehrhart
AU - Rohit G Jadhav
AU - Amitava Choudhury
AU - Pericles Stavropoulos
PY - 2026
DA - 2026/10/01
JO - Inorganic chemistry
DO - 10.1021/acs.inorgchem.6c02795
UR - https://europepmc.org/article/MED/42831556
AB - A tetraamido macrocyclic ligand scaffold (L1H4) has been synthesized and metalated with Co(III) to afford anionic metal complexes [CoIII(L1)]- (cations: K+, PPh4+) that are paramagnetic (S = 1) in solution and display semi-reversible reduction waves (CoII/III) and irreversible anodic events in cyclic voltammograms. These macrocyclic Co(III) compounds have been examined as nitrene-transfer catalysts, involving iminoiodinane precursors (PhI=NR) and olefins, to reveal efficient aziridinations and/or allylic aminations, especially with sterically unencumbered styrenes. Mechanistic studies indicate that stepwise formation of two N-C bonds is operative in aziridinations, in which both polar and radical contributions are evident, in contrast to analogous nitrene-transfer chemistry displayed by [CoIII(TAMLred)]-, the latter relying on single-electron transfer between ligand and substrate. The generation of both mono- and bis-nitrene cobalt complexes or derivatives is indicated by ESI-MS, but their precise structural identity, electronic configuration, and relevance in nitrene-transfer chemistry remains an area for further exploration.
SN - 0020-1669
SN - 1520-510X
ER -