Selective C−H Functionalization of Methane and Ethane by a Molecular SbV Complex

Owing to the strong nonpolar bonds involved, selective C?H functionalization of methane and ethane to esters remains a challenge for molecular homogeneous chemistry. We report that the computationally predicted main‐group p‐block Sb^V(TFA)₅ complex selectively functionalizes the C?H bonds of methane and ethane to the corresponding mono and/or diol trifluoroacetate esters at 110–180 °C with yields for ethane of up to 60 % with over 90 % selectivity. Experimental and computational studies support a unique mechanism that involves Sb^V‐mediated C?H activation followed by functionalization of a Sb^V‐alkyl intermediate.