Dehydrogenative Double C−H Bond Activation in a Germylene-Rhodium Complex

Transition metal tetrylene complexes offer great opportunities for molecular cooperation due to the ambiphilic character of the group 14 element. Here we focus on the coordination of germylene [(ArMes2)2Ge :] (ArMes=C6H3-2,6-(C6H2-2,4,6-Me3)2) to [RhCl(COD)]2 (COD=1,5-cyclooctadiene), which yields a...

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Detalles Bibliográficos
Autores: Bajo Velázquez, Sonia, Alcaide, María M., López Serrano, Joaquín, Campos, Jesús
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2021
País:España
Institución:Universidad de Sevilla (US)
Repositorio:idUS. Depósito de Investigación de la Universidad de Sevilla
OAI Identifier:oai:idus.us.es:11441/134927
Acceso en línea:https://hdl.handle.net/11441/134927
https://doi.org/10.1002/chem.202102529
Access Level:acceso abierto
Descripción
Sumario:Transition metal tetrylene complexes offer great opportunities for molecular cooperation due to the ambiphilic character of the group 14 element. Here we focus on the coordination of germylene [(ArMes2)2Ge :] (ArMes=C6H3-2,6-(C6H2-2,4,6-Me3)2) to [RhCl(COD)]2 (COD=1,5-cyclooctadiene), which yields a neutral germyl complex in which the rhodium center exhibits both η6- and η2-coordination to two mesityl rings in an unusual pincer-type structure. Chloride abstraction from this species triggers a singular dehydrogenative double C−H bond activation across the Ge/Rh motif. We have isolated and fully characterized three rhodium-germyl species associated to three C−H cleavage events along this process. The reaction mechanism has been further investigated by computational means, supporting the key cooperative action of rhodium and germanium centers.