An Escape from Noble Metals for Generating Urethanes via Reductive Carbonylation of Nitroarenes over FeSe2/γ-Al2O3 †

The reaction of FeCl3, SeO2, and Pyridine (Py) in the presence of methanol (MeOH) under CO pressure generates a black precipitate, which has been confirmed as ferric di-selenide, FeSe2 through different structure characterization methods. Furthermore, impregnation of 5 wt% of FeSe2 onto γ-Al2O3 exhibits better catalytic performance than FeSe2 due to the highly dispersed and smaller particle sizes ca. 200–300 nm. The reductive carbonylation of nitrobenzene (NB) was investigated over FeSe2/γ-Al2O3 as a heterogeneous catalyst, delivering an excellent yield and high selectivity of methyl-N-phenyl carbamate (MPC). Moreover, a set of reactions was performed with variation in the reaction time, temperature, and pressure to investigate the effects of these factors. In particular, FeSe2/γ-Al2O3 is highly stable and can be recycled for up to five cycles without significant loss in catalytic performance. A mechanistic study was also conducted on this low-cost catalyst system, especially proposing a crucial role of FeSe2 (μ-CO) active species.