Selective C-H Functionalization of Methane and Ethane by a Molecular Sb 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 (TFA) 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 -mediated C-H activation followed by functionalization of a Sb -alkyl intermediate.