Transfer hydrogenation of nitroarenes with hydrazine at near-room temperature catalysed by a MoO₂ catalyst

We present an experimental and computational study of the elementary steps of hydrazine hydrogen transfer on crystalline MoO₂, and demonstrate its unique bifunctional metallic-basic properties in a catalytic hydrogenation reaction. Density functional theory (DFT) calculations suggest that the stepwise hydrogen transfer via the prior cleavage of the N–H bond rather than the N–N bond, is the key step to create the dissociated hydride and proton species on the dual Mo and O sites, marking its difference with common oxides. Crystalline MoO₂ shows exceptionally high chemoselectivity toward the nitro reduction over CC, CC, and CN groups at room temperature and lower, down to 0 °C, rendering it as a promising catalytic material for hydrogenation reactions.