Metal‐Mediated Production of Isocyanates, R3ENCO from Dinitrogen, Carbon Dioxide, and R3ECl

A highly efficient and versatile chemical cycle has been developed for the production of isocyanates through the molecular fixation of N2 , CO2 and R3 ECl (E=C, Si, and Ge). Key steps include a 'one-pot' photolytic N-N bond cleavage of a Group 6 dinuclear dinitrogen complex with in situ trapping by R3 ECl to provide a metal terminal imido complex that can engage in simultaneous nitrene-group transfer and oxygen-atom transfer to generate an intermediate metal terminal oxo complex with release of the isocyanate product. Reaction of the oxo complex with additional equivalents of R3 ECl regenerates a metal dichloride that is the precursor for dinuclear dinitrogen starting material.