Deoxygenation of Nitrous Oxide and Nitro Compounds Using Bis(N‐Heterocyclic Silylene)Amido Iron Complexes as Catalysts

Herein, we report the efficient degradation of N2O with a well‐defined bis(silylene)amido iron complex as catalyst. The deoxygenation of N2O using the iron silanone complex 4 as a catalyst and pinacolborane (HBpin) as a sacrificial reagent proceeds smoothly at 50 °C to form N2, H2, and (pinB)2O. Mechanistic studies suggest that the iron–silicon cooperativity is the key to this catalytic transformation, which involves N2O activation, H atom transfer, H2 release and oxygenation of the boron sites. This approach has been further developed to enable catalytic reductions of nitro compounds, producing amino‐boranes with good functional‐group tolerance and excellent chemoselectivity. The efficient catalytic degradation of N2O to N2 by well‐defined bis(silylene)amido iron complexes under mild conditions involving the cooperative effect between the iron and silylene ligands is reported. Selective reductions of nitro compounds to amino‐boranes with good functional‐group tolerance and excellent chemo‐selectivity have been developed using the same approach.