Selective C−H Functionalization of Methane and Ethane by a Molecular Sb V 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.