Platinum−Germanium Compounds from the Reactions of (COD)PtMe₂ (COD = 1,5-cyclooctadiene) with HGePh₃

The reaction of Pt(COD)Me2 with HGePh3 in hexane solvent at room temperature for 30 h yielded the two new compounds Pt(COD)(Me)(GePh3), 1 (16%), and Pt(COD)(GePh3)2, 2 (9%), by replacement of the methyl groups by GePh3 ligands. When this reaction was performed under an atmosphere of CO the compound trans-Pt(CO)2(GePh3)2, 3 was obtained in 26% yield together with a new compound Pt2(CO)2(GePh3)2(μ-GePh2)2, 4 in 10% yield. Compound 2 was obtained from 1 in 51% yield by reaction with an additional quantity of HGePh3 and 3 was obtained from 2 in 16% yield by treatment with CO. All four products were characterized by single crystal X-ray diffraction analyses. Compound 4 contains two platinum atoms with two bridging GePh2 ligands and a Pt−Pt single bond. Fenske−Hall molecular orbital calculations on a model for 4 were performed to understand its bonding.