Organogallium- and organozinc-rich palladium and platinum clusters

The heteroleptic, binuclear compounds [M-2(GaCp*)(3)(PMe3)(2)] (M = Pd: 1a, Pt: 1b, Cp* = pentamethyl-cyclopentadienyl) can be obtained if [Pd-2(dvds)(3)] (dvds = 1,3-divinyl-1,1,3,3-tetramethyldisiloxane) or [Pt(COD)(2)] (COD = cyclooctadiene) were treated with a 3 : 2 ratio of GaCp* and PMe3. A trinuclear complex [Pd-3(GaCp*)(3)(PMe3)(3)] (2) was isolated from in situ prepared [Pd(PMe3)(2)Me-2] and treatment with GaCp*. The new complexes were used as starting compounds for selective Ga/Zn exchange reactions to afford the dinuclear palladium compound [Pd-2(ZnCp*)(ZnMe)(3)(PMe3)(5)] (3a) and the mononuclear platinum compound [Pt(ZnCp*)(2)(ZnMe)(2)(PMe3)(2)] (3b). The effects of a final transition metal count in organozinc ligated compounds and stabilization of Lewis acidic fragments like [Pd(PPh3)(3)], [Ni(C2H4)(3)] or [Mo(CO)(5)] were presented and discussed. All compounds have been fully characterized by H-1, C-13, and P-31 NMR spectroscopy, mass spectrometry using a liquid injection field desorption ionization (LIFDI) method, elemental analysis, and single crystal X- ray diffraction studies and the coordination polyhedra were analysed by the method of continuous shape measure (CShM).