Issue 4, 2022

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

Abstract

We herein present an efficient approach for the chemoselective synthesis of arylamines from nitroarenes and hydrazine over an iron-molybdenum sulfide catalyst ([FeMo]Sx). The heterogeneous hydrogen transfer reduction can be efficiently carried out at 30 °C and provides anilines with 95–99% selectivities. The in situ gas product analysis demonstrates that [FeMo]Sx can catalyze the decomposition of N2H4 to H* species, not H2. 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 (Hδ− and Hδ+). These findings will provide a novel route for the synthesis of substituted anilines and broaden the application of MoSx catalysts under mild conditions.

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

Supplementary files

Article information

Article type
Paper
Submitted
14 Sep 2021
Accepted
09 Dec 2021
First published
06 Jan 2022

Dalton Trans., 2022,51, 1553-1560

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

S. Li, Z. Huang, H. Liu, M. Liu, C. Zhang and F. Wang, Dalton Trans., 2022, 51, 1553 DOI: 10.1039/D1DT03107D

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