The Bis(pentafluoroethyl)germylene Trimethylphosphane Adduct (C2 F5 )2 Ge⋅PMe3 : Characterization, Ligand Properties,...

The synthesis of the germylene phosphane adduct (C2 F5 )2 Ge⋅PMe3 is described. Starting from (C2 F5 )3 GeH in an excess of PMe3 , heating was applied, whereupon reductive elimination of C2 F5 H occurred. The molecular structure was ascertained by X-ray diffraction and compared with information obtained by quantum chemical methods. The ligand properties were derived by studying the IR spectrum of the nickel(0) complex [Ni(CO)3 {Ge(C2 F5 )2 (PMe3 )}] in the CO region. (C2 F5 )2 Ge⋅PMe3 turned out to be a π-accepting ligand comparable to PMe3 , in terms of Tolman's electronic parameter. Furthermore a [2+4] cycloaddition reaction with 2,3-dimethyl-1,3-butadiene, and σ-bond insertion reactions were recorded. Activation of the C-Cl bond in dichloromethane gives rise to the formation of the phosphonium ylide complex [(C2 F5 )2 Cl2 Ge-CH2 PMe3 ], which was fully characterized by X-ray diffraction.