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

The reaction of Pt(COD)Me(2) with HGePh(3) in hexane solvent at room temperature for 30 h yielded the two new compounds Pt(COD)(Me)(GePh(3)), 1 (16%), and Pt(COD)(GePh(3))(2), 2 (9%), by replacement of the methyl groups by GePh(3) ligands. When this reaction was performed under an atmosphere of CO the compound trans-Pt(CO)(2)(GePh(3))(2), 3 was obtained in 26% yield together with a new compound Pt(2)(CO)(2)(GePh(3))(2)(mu-GePh(2))(2), 4 in 10% yield. Compound 2 was obtained from 1 in 51% yield by reaction with an additional quantity of HGePh(3) 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 GePh(2) ligands and a Pt-Pt single bond. Fenske-Hall molecular orbital calculations on a model for 4 were performed to understand its bonding.