Metal-free dehydrogenation of formic acid to H(2) and CO(2) using boron-based catalysts

Formic acid is at the crossroads of novel sustainable energy strategies because it is an efficient H(2) carrier. Yet, to date, its decomposition to H(2) relies on metal-based catalysts. Herein, we describe the first metal-free catalysts able to promote the dehydrogenation of formic acid. Using dialkylborane derivatives, HCOOH is decomposed to H(2) and CO(2) in the presence of a base with high selectivity. Experimental and computational results point to the involvement of bis(formyloxy)borates as key intermediates in the C–H bond activation of a formate ligand.