E ^II /E ^IV O (E = Ge, Sn) Catalyzed Nitrous Oxide Activation and Chemodivergent Reduction of Nitroarenes

Abstract While homogeneous catalysis remains predominantly dominated by transition metal complexes, the utilization of main group compounds as redox catalysts for diverse chemical transformations represents a long‐sought yet underexplored frontier. This work reports the catalytic reduction of N 2 O in the presence of HBpin via an unprecedented E II /E IV O (E = Ge, Sn) redox platform, employing carbodiphosphorane ligated germylene or stannylene as the catalyst. The key Ge IV and Sn IV ‐oxo intermediates have been isolated and characterized. Furthermore, we extend this redox platform to achieve efficient and chemodivergent reduction of nitroarenes under mild conditions. Notably, through systematic modulation of reaction conditions, four different reduced products including amino, hydroxylamine, azoxy, and hydrazine derivatives can be synthesized from nitroarenes with high yields and selectivity. This work establishes a novel heavy group 14 element‐based catalytic manifold and unlocks new opportunities for the application of heavy carbene analogues in redox catalysis.