Abstract
Cobalt-catalyzed C-H amination via M-nitrenoid species is spiking the interest of the research community. Understanding this process at a molecular level is a challenging task, and here we report a well-defined macrocyclic system featuring a pseudo-Oh aryl-CoIII species that reacts with aliphatic azides to effect intramolecular Csp2-N bond formation. Strikingly, a putative aryl-CoNR nitrenoid intermediate species is formed and is rapidly trapped by a carboxylate ligand to form a carboxylate masked-nitrene, which functions as a shortcut to stabilize and guide the reaction to productive intramolecular Csp2-N bond formation. On one hand, several intermediate species featuring the Csp2-N bond formed have been isolated and structurally characterized, and the essential role of the carboxylate ligand has been proven. Complementarily, a thorough density functional theory study of the Csp2-N bond formation mechanism explains at the molecular level the key role of the carboxylate-masked nitrene species, which is essential to tame the metastability of the putative aryl-CoIIINR nitrene species to effectively yield the Csp2-N products. The solid molecular mechanistic scheme determined for the Csp2-N bond forming reaction is fully supported by both experimental and computation complementary studies.
Original language | English |
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Journal | INORGANIC CHEMISTRY |
DOIs | |
Publication status | Accepted in press - 2022 |
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CCDC 2097546: Experimental Crystal Structure Determination
Capdevila, L. (Creator), Montilla, M. (Contributor), Planas, O. (Contributor), Brotons, A. (Contributor), Salvador, P. (Contributor), Martin-Diaconescu, V. (Contributor), Parella, T. (Contributor), Luis, J. M. (Contributor) & Ribas, X. (Contributor), Cambridge Crystallographic Data Centre, 14 Jan 2022
DOI: 10.5517/ccdc.csd.cc28dns4, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc28dns4&sid=DataCite
Dataset
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CCDC 2097543: Experimental Crystal Structure Determination
Capdevila, L. (Creator), Montilla, M. (Contributor), Planas, O. (Contributor), Brotons, A. (Contributor), Salvador, P. (Contributor), Martin-Diaconescu, V. (Contributor), Parella, T. (Contributor), Luis, J. M. (Contributor) & Ribas, X. (Contributor), Cambridge Crystallographic Data Centre, 19 Jul 2021
DOI: 10.5517/ccdc.csd.cc28dnp1, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc28dnp1&sid=DataCite
Dataset
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CCDC 2097545: Experimental Crystal Structure Determination
Capdevila, L. (Contributor), Montilla, M. (Contributor), Planas, O. (Contributor), Brotons, A. (Contributor), Salvador, P. (Contributor), Martin-Diaconescu, V. (Contributor), Parella, T. (Contributor), Luis, J. M. (Contributor) & Ribas, X. (Contributor), Cambridge Crystallographic Data Centre, 19 Jul 2022
DOI: 10.5517/ccdc.csd.cc28dnr3, https://www.ccdc.cam.ac.uk/structures/search?id=doi:10.5517/ccdc.csd.cc28dnr3&sid=DataCite
Dataset