Reductive Elimination and Oxidative Addition of Hydrogen at Organostannylium and Organogermylium Cations

Abstract

Bulkily substituted organodihydrogermylium and -stannylium cations [Ar*EH₂ ]⁺ (E=Ge, Sn; Ar*=2,6-Trip₂ C₆ H₃ , Trip=2,4,6-triisopropylphenyl) were characterized as salts of the weakly coordinating perfluorinated alkoxyaluminate anion [Al{OC(CF₃ )₃ }₄ ]^- . At room temperature, the stannylium cation liberates hydrogen to generate the low valent organotin cation [Ar*Sn]⁺ . In contrast, the dihydrogermylium cation transfers the hydrogen atoms to an aryl moiety of the terphenyl ligand and oxidatively adds either hydrogen under an atmosphere of hydrogen or a sp² CH unit of the 1,2-difluorobenzene solvent.

Keywords: germylium cation; hydrogen activation; oxidative addition; reductive elimination; stannylium cation.