Flash Communication: Strained and Bimetallic Structures of Rhodium and Iridium Germyl Complexes with Phosphinoamido Ligands
In the coordination chemistry of heavier tetrylenes (:ER<sub>2</sub>, where E = Si, Ge, Sn, Pb), chelating P,N-donor ligands occupy a privileged position, though phosphinoamido ligands, [R<sub>2</sub>P–NR′]<sup>−</sup>, have been barely investigated. Herein, we re...
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2025
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| Sažetak: | In the coordination chemistry of heavier tetrylenes (:ER<sub>2</sub>, where E = Si, Ge, Sn, Pb), chelating P,N-donor ligands occupy a privileged position, though phosphinoamido ligands, [R<sub>2</sub>P–NR′]<sup>−</sup>, 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 [MCl<sub>2</sub>Cp*]<sub>2</sub> precursors (Cp* = η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>). At variance, [MCl(COD)]<sub>2</sub> 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. |
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