Organogallium- and organozinc-rich palladium and platinum clusters

The heteroleptic, binuclear compounds [M2(GaCp*)3(PMe3)2] (M = Pd: 1a, Pt: 1b, Cp* = pentamethylcyclopentadienyl) can be obtained if [Pd2(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 [Pd3(GaCp*)3(PMe3)3] (2) was isolated from in situ prepared [Pd(PMe3)2Me2] and treatment with GaCp*. The new complexes were used as starting compounds for selective Ga/Zn exchange reactions to afford the dinuclear palladium compound [Pd2(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 (1)H, (13)C, and (31)P 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).