Nucleophilic Substitution at Difluoro-Carbene Complexes of the Coinage Metals
- 1Université de Toulouse, CNRS , , UMR 5069, 118 Route de Narbonne , Cedex 09,
- 2Université de Pau et des Pays de l’Adour, CNRS , , UMR 5254, Hélioparc, 2 Avenue du Président Angot, Cedex 09 , ,
- 3Université de Toulouse, CNRS , , UAR 2599), 118 Route de Narbonne , Cedex 09,
Abstract
Carbene functionalization through direct substitution at the carbene center is well established for Fischer-type carbene complexes of early transition metals but remains exceedingly rare for carbene complexes of late transition metals. Here, we report a general strategy for carbene functionalization at coinage metals based on nucleophilic substitution of difluorocarbene complexes. Persistent LnAu(I)=CF2+ complexes undergo efficient fluorine-to-nitrogen and fluorine-to-oxygen substitution with nucleophiles, providing direct access to fluoro-amino- and fluoro-oxy-carbene complexes. The methodology is also applicable to transient Au(I) difluorocarbenes and extends to Cu(I) and Ag(I) systems, enabling carbene functionalization across the coinage metal series. Access to a family of closely related group 11 carbenes (10 examples) enables direct comparison of their structure and bonding. Spectroscopic and computational studies reveal that fluorine-to-nitrogen substitution profoundly impacts the electronic structure of the carbene complex, affording species best described as metalated fluoro-iminium ions. Density functional theory supports a highly exergonic addition−elimination mechanism driven by Si−F bond formation and identifies metal-to-carbene π-backdonation as the key factor governing the stability of difluorocarbene intermediates, following the trend Au > Cu > Ag. These findings establish nucleophilic substitution as a general strategy for the functionalization of coinage-metal carbene complexes and demonstrate that heteroatom substitution provides direct access to electronically distinct metalated iminium and oxonium species.
Versions
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BibTeX
@article{vesseur2026nucleophilic,
title = {{Nucleophilic Substitution at Difluoro-Carbene Complexes of the Coinage Metals}},
author = {David Vesseur and Shuo Li and Juan Carlos Pérez-Sánchez and Nina Albouy and Sonia Mallet-Ladeira and Karinne Miqueu and Didier Bourissou},
journal = {JACS Au},
year = {2026},
month = nov,
doi = {10.1021/jacsau.6c00964},
url = {https://pubs.acs.org/jaaucr/article/doi/10.1021/jacsau.6c00964/5465164/Nucleophilic-Substitution-at-Difluoro-Carbene},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - JOUR
TI - Nucleophilic Substitution at Difluoro-Carbene Complexes of the Coinage Metals
AU - David Vesseur
AU - Shuo Li
AU - Juan Carlos Pérez-Sánchez
AU - Nina Albouy
AU - Sonia Mallet-Ladeira
AU - Karinne Miqueu
AU - Didier Bourissou
PY - 2026
DA - 2026/11/05
JO - JACS Au
DO - 10.1021/jacsau.6c00964
UR - https://pubs.acs.org/jaaucr/article/doi/10.1021/jacsau.6c00964/5465164/Nucleophilic-Substitution-at-Difluoro-Carbene
AB - Carbene functionalization through direct substitution at the carbene center is well established for Fischer-type carbene complexes of early transition metals but remains exceedingly rare for carbene complexes of late transition metals. Here, we report a general strategy for carbene functionalization at coinage metals based on nucleophilic substitution of difluorocarbene complexes. Persistent LnAu(I)=CF2+ complexes undergo efficient fluorine-to-nitrogen and fluorine-to-oxygen substitution with nucleophiles, providing direct access to fluoro-amino- and fluoro-oxy-carbene complexes. The methodology is also applicable to transient Au(I) difluorocarbenes and extends to Cu(I) and Ag(I) systems, enabling carbene functionalization across the coinage metal series. Access to a family of closely related group 11 carbenes (10 examples) enables direct comparison of their structure and bonding. Spectroscopic and computational studies reveal that fluorine-to-nitrogen substitution profoundly impacts the electronic structure of the carbene complex, affording species best described as metalated fluoro-iminium ions. Density functional theory supports a highly exergonic addition−elimination mechanism driven by Si−F bond formation and identifies metal-to-carbene π-backdonation as the key factor governing the stability of difluorocarbene intermediates, following the trend Au > Cu > Ag. These findings establish nucleophilic substitution as a general strategy for the functionalization of coinage-metal carbene complexes and demonstrate that heteroatom substitution provides direct access to electronically distinct metalated iminium and oxonium species.
SN - 2691-3704
ER -