Activation of Protic, Hydridic and Apolar E-H Bonds by a Boryl-Substituted Ge^II Cation

The synthesis of a boryl-substituted germanium(II) cation, [Ge{B(NDippCH)₂ }(IPrMe)]⁺ , (Dipp=2,6-diisopropylphenyl) featuring a supporting N-heterocyclic carbene (NHC) donor, has been explored through chloride abstraction from the corresponding (boryl)(NHC)GeCl precursor. Crystallographic studies in the solid state and UV/Vis spectra in fluorobenzene solution show that this species dimerizes under such conditions to give [(IPrMe){(HCNDipp)₂ B}Ge=Ge{B(NDippCH)₂ }(IPrMe)]²⁺ (IPrMe = 1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene), which can be viewed as an imidazolium-functionalized digermene. The dimer is cleaved in the presence of donor solvents such as [D₈ ]thf or [D₅ ]pyridine, to give monomeric adducts of the type [Ge{B(NDippCH)₂ }(IPrMe)(L)]⁺ . In the case of the thf adduct, the additional donor is shown to be sufficiently labile that it can act as a convenient in situ source of the monomeric complex [Ge{B(NDippCH)₂ }(IPrMe)]⁺ for oxidative bond-activation chemistry. Thus, [Ge{B(NDippCH)₂ }(IPrMe)(thf)]⁺ reacts with silanes and dihydrogen, leading to the formation of Ge^IV products, whereas the cleavage of the N-H bond in ammonia ultimately yields products containing C-H and B-N bonds. The facile reactivity observed in E-H bond activation is in line with the very small calculated HOMO-LUMO gap (132 kJ mol^-1 ).