Platinum Complexes Bearing a Tripodal Germyl Ligand

The reaction of the germane [Ge(H)(2-C6H4PPh2)3] (1) and the platinum precursor complex [Pt(nbe)3] (nbe = norbornene) gave a racemic mixture of the germyl complex [Pt(nor){Ge(2-C6H4PPh2)3}] (2; nor = exo-2-norbornyl, exo-2-bicyclo[2.2.1]heptyl). Mechanistic studies showed that the hydrido complex [Pt(H){Ge(2-C6H4PPh2)3}] (3) is not formed as an intermediate during the formation of 2. Further studies revealed that in contrast to the chlorido complex [Pt(Cl){Ge(2-C6H4PPh2)3}] (4), the methyl compound [Pt(CH3){Ge(2-C6H4PPh2)3}] (5) is an efficient starting compound for accessing cationic platinum species. Complex 5 was converted into the triflato complex [Pt(OTf){Ge(2-C6H4PPh2)3}] (6) as well as the complexes [Pt(L){Ge(2-C6H4PPh2)3}][B{3,5-C6H3(CF3)2}4] [L = thf (7), toluene (8), CH2Cl2 (9), PPh3 (10)].