An efficient synthesis of 2-di-tert-butylphosphanylmethylpyrrole (HpyrmPtBu(2)), by treating 2-dimethylaminomethylpyrrole (HpyrmNMe(2)) with tBu(2)PH at 135 degrees C in the absence of any solvent, has allowed the preparation of the new PGeP germylene Ge(pyrmPtBu(2))(2) (1), by treating [GeCl2(dioxane)] with LipyrmPtBu(2), in which the Ge atom is stabilized by intramolecular interactions with one (solid state) or both (solution) of its phosphane groups. Reactions of germylene 1 with Group 10 metal dichlorido complexes containing easily displaceable ligands have led to [MCl{kappa P-3,Ge,P-GeCl(pyrmPtBu(2))(2)}] [M=Ni (2), Pd (3), Pt (4)], which have an unflawed square-planar metal environment. Treatment of germylene 1 with [AuCl(tht)] (tht=tetrahydrothiophene) rendered [Au{kappa P-3,Ge,P-GeCl(pyrmPtBu(2))(2)}] (5), which is a rare case of a T-shaped gold(I) complex. The hydrolysis of 5 gave the linear gold(I) derivative [Au(kappa P-HpyrmPtBu(2))(2)]Cl (6). Complexes 2-5 contain a PGeP pincer chloridogermyl ligand that arises from the insertion of the Ge atom of germylene 1 into a M-Cl bond of the corresponding metal reagent. The bonding in these molecules has been studied by DFT/NBO/QTAIM calculations. These results demonstrate that the great flexibility of germylene 1 makes it a better precursor to PGeP pincer complexes than the previously known germylenes of this type.
