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 SbV(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 SbV‐mediated C−H activation followed by functionalization of a SbV‐alkyl intermediate. The high‐oxidation‐state complex SbV(TFA)5 is capable of selective C−H functionalization of methane and ethane to their corresponding mono and/or diol trifluoroacetate esters. Experimental and computational studies support a unique C−H activation mechanism mediated by SbV, which is then followed by functionalization of an organoantimony intermediate.