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 compl...

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Bibliographic Details
Authors: Bajo, Sonia, Fernández-Buenestado, Marta, López-Serrano, Joaquín, Campos, Jesús
Format: article
Status:Published version
Publication Date:2025
Country:España
Institution:Consejo Superior de Investigaciones Científicas (CSIC)
Repository:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/414463
Online Access:http://hdl.handle.net/10261/414463
https://api.elsevier.com/content/abstract/scopus_id/105024756264
Access Level:Open access
Description
Summary: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 π-backbonding.