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Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido
Sonia Bajo1, Marta Fernández-Buenestado1, Joaquín López-Serrano1
1Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Consejo Superior de Investigaciones Científicas (CSIC) and Universidad de Sevilla, Avenida Américo Vespucio 49, 41092 Sevilla, Spain.
None:
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.
