Transition-Metal-Mediated Germanium–Fluorine Activation: Inverse Electron Flow in σ‑Bond Metathesis

We report the first example of Ge–F activation using a transition metal complex, in which σ-bond metathesis between Ge–F and Ir–H σ-bonds takes place with a specific electron flow. Unexpected selectivity for Ge–F over Ge–CPh σ-bond activation is observed. Density functional theory suggests that a strong dative Ir→Ge interaction, which efficiently weakens the σ-bond, helps electrostatically the coupling between the (δ−) fluorine on Ge and the (δ+) hydrogen on Ir, making Ge–F bond activation very easy.