Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido Ligands

In the coordination chemistry of heavier tetrylenes (:ER2, where E = Si, Ge, Sn, Pb), chelating P,N-donor ligands occupy a privileged position, though phosphinoamido ligands, [R2P−NR′] −, have been barely investigated. Herein, we report the synthesis and structural characterization of such complexes...

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Detalles Bibliográficos
Autores: Bajo Velázquez, Sonia, Fernández Buenestado, Marta, López Serrano, Joaquín, Campos, Jesús
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2025
País:España
Institución:Universidad de Sevilla (US)
Repositorio:idUS. Depósito de Investigación de la Universidad de Sevilla
OAI Identifier:oai:idus.us.es:11441/181609
Acceso en línea:https://hdl.handle.net/11441/181609
https://doi.org/10.1021/acs.organomet.5c00403
Access Level:acceso abierto
Descripción
Sumario:In the coordination chemistry of heavier tetrylenes (:ER2, where E = Si, Ge, Sn, Pb), chelating P,N-donor ligands occupy a privileged position, though phosphinoamido ligands, [R2P−NR′] −, have been barely investigated. Herein, we report the synthesis and structural characterization of such complexes, whose structures drastically differ depending on the group 9 metal precursor used. Strained four-membered {P−N−Ge−M} metallacycles (M = Rh, Ir) are produced from the reaction of phosphinoamido germylenes with [MCl2Cp*]2 precursors (Cp* = η5 -C5Me5). At variance, [MCl(COD)]2 dimers are not broken apart; instead, they afford bimetallic species featuring bridging phosphinoamido−germyl and chloride ligands between the two metals. All new compounds were isolated on a preparative scale and spectroscopically characterized and their structures confirmed by X-ray diffraction. Computational studies support the σ-donor character of the Ge−M interaction and the absence of significant πbackbonding.