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 CO2 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.
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