Divergent deazotation and nitrene group transfer pathways at cobalt phospha-triazene species

Abstract

Metal-nitrenes are critical intermediates in the incorporation of nitrogen functional groups, and a better understanding of the mechanism of their formation from the corresponding organoazide adducts is highly desirable. In this work, we demonstrate a new mode of organoazide deazotation at a phosphide-containing (PPP)Co scaffold. A dimeric cobalt species reacts with organoazides to furnish the corresponding cobalt(II) phosphazido complexes via selective [2 + 3] cycloaddition. This metal–ligand cooperative (MLC) transformation involves P–P bond cleavage along with Co–Nα and P–Nγ bond formation, revealing that the Co-phosphide site acts as an anchoring site for organoazide binding. The reduced Co(I) phosphazido complexes react with electrophiles such as B(C6F5)3 and methylating reagents at the Nγ position to give the respective borane adduct and methyl species. The electrophilic functionalization of such anchored organoazide moieties leads to a significantly less delocalized azide moiety and elongation of the Nβ–Nγ distance, rendering it susceptible toward thermolytic Nβ–Nγ bond cleavage. The resulting nitrene moiety reacts with the phosphide moiety or with exogenous nitriles to form the respective iminophosphide or phospha-amidinate species. Such reactivity provides a new mode of organoazide activation via formation of a dialkyl phospha-triazene species, distinct from previous studies that primarily feature Nα–Nβ bond cleavage.

Graphical abstract: Divergent deazotation and nitrene group transfer pathways at cobalt phospha-triazene species

Supplementary files

Article information

Article type
Research Article
Submitted
20 Jun 2025
Accepted
08 Jul 2025
First published
10 Jul 2025

Inorg. Chem. Front., 2025, Advance Article

Divergent deazotation and nitrene group transfer pathways at cobalt phospha-triazene species

K. Lee, S. Kim and Y. Lee, Inorg. Chem. Front., 2025, Advance Article , DOI: 10.1039/D5QI01338K

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