Polar hydrogen species mediated nitroarenes selective reduction to anilines over an [FeMo]Sx catalyst

We herein present an efficient approach for the chemoselective synthesis of arylamines from nitroarenes and hydrazine over an iron-molybdenum sulfide catalyst ([FeMo]S-x). The heterogeneous hydrogen transfer reduction can be efficiently carried out at 30 degrees C and provides anilines with 95-99% selectivities. The in situ gas product analysis demonstrates that [FeMo]S-x can catalyze the decomposition of N2H4 to H* species, not H-2. Combining with the kinetic analysis of the aniline generation rates from nitrobenzene and intermediates, the nitro group reduction to the nitroso group is confirmed to be the rate-determining step. The positive slope of Hammett's equation suggests that the critical intermediate in the rate-determining step is in the negative state, which suggests that the active H* should be in polar states (H delta- and H delta+). These findings will provide a novel route for the synthesis of substituted anilines and broaden the application of MoSx catalysts under mild conditions.

Automated summary

An efficient approach for the synthesis of arylamines from nitroarenes and hydrazine using an iron-molybdenum sulfide catalyst has been presented. The study reveals that the reduction of the nitro group to the nitroso group is the rate-determining step, and it is confirmed that the active H* should be in polar states.