Unambiguous Spectroscopic Characterization of a Gold Difluorocarbene

Gold(I) carbenes, defined as [LAu═CR2]+, are key intermediates in catalysis. Their isolation is challenging due to the high electrophilic character of the carbene that cannot be tempered solely by π-backdonation from gold. Among those, the simple difluorocarbene complex has been invoked in several s...

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Detalhes bibliográficos
Autores: Navarro Blasco, Miquel, Delaurenti ,Louise, Pita-Milleiro, Alejandra, Campos, Jesús
Formato: artículo
Fecha de publicación:2025
País:España
Recursos:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/727280
Acesso em linha:https://hdl.handle.net/10486/727280
https://dx.doi.org/10.1021/jacsau.5c00911
Access Level:acceso abierto
Palavra-chave:Carbene
alkylidene
gold(I)
bulkyphosphine
fluorine
ligandcavity
Química
Descrição
Resumo:Gold(I) carbenes, defined as [LAu═CR2]+, are key intermediates in catalysis. Their isolation is challenging due to the high electrophilic character of the carbene that cannot be tempered solely by π-backdonation from gold. Among those, the simple difluorocarbene complex has been invoked in several studies, but attempts to isolate it have failed, while its identification remains questionable. In this study, we report the unambiguous spectroscopic characterization of the gold difluorocarbene complex [P–Au═CF2]+, providing key insights into its structural and electronic features. The kinetic stabilization of the carbene was only possible owing to the shielding offered by a congested and cavity-shaped phosphine that prevents decomposition under strict anhydrous conditions. Besides, the nature of the anion is key to provide further thermal stability for prolonged times