Characterization of Iminobismuthanes and Catalytic Reduction of Organic Azides via Bi(I)/Bi(III) Redox Cycling

We report the stoichiometric and catalytic reactivity of organobismuth(I) complexes with organic azides. Treatment of N,C,N ‐pincer bismuthinidenes with organic azides (acyl, sulfonyl, and bulky aryl) results in monomeric iminobismuthanes which can be structurally characterized —including the formal Bi=N double bond— by multinuclear NMR spectroscopy and single‐crystal X‐ray diffraction. Building upon the stoichiometric reactivity of the monomeric iminobismuthanes, catalytic reduction of a broad range of organic azides is developed. DFT calculations of the catalytic reaction pathway support the redox nature of the overall process.