Harnessing the Unique Reactivity of an Exceedingly Low-Coordinate Platinum(0)-Germylene System for E–H (E = H, N, O) Bond Activation and Catalytic Hydrodehalogenation Reactions

Pairing transition metals and heavier tetrylenes (Si, Ge, Sn, Pb) holds great potential for cooperative bond activation and catalysis. In this work, we investigate the reactivity of an exceptionally low-coordinate Pt(0)/Ge(II) system that emerges from the reaction between the monoligated platinum(0) precursor [(PMe2ArDipp2)Pt(olefin)] with Power’s germylene dimer [ArDipp2GeCl]2 (where ArDipp2 = C6H3-2,6-(C6H3-2,6-iPr2)2)). The resulting complex revealed a unique ability for cooperative bond activation. Stoichiometric reactions with dihydrogen, water, and ammonia unveil the formation of Pt(II)-germyl compounds, characterized by distinct isomeric forms, whose flexibility derives from the particularly low-coordination. Its catalytic potential is explored in the hydrodehalogenation of aliphatic halides under dihydrogen atmosphere, demonstrating promising conversions even for inert alkyl halides.