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Metal-Mediated Production of Isocyanates, R3ENCO from Dinitrogen, Carbon Dioxide, and R3ECl
Ist Teil von
Angewandte Chemie (International ed.), 2015-08, Vol.54 (35), p.10220-10224
Ort / Verlag
Weinheim: WILEY-VCH Verlag
Erscheinungsjahr
2015
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
A highly efficient and versatile chemical cycle has been developed for the production of isocyanates through the molecular fixation of N2, CO2 and R3ECl (E=C, Si, and Ge). Key steps include a ‘one‐pot’ photolytic NN bond cleavage of a Group 6 dinuclear dinitrogen complex with in situ trapping by R3ECl 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 R3ECl regenerates a metal dichloride that is the precursor for dinuclear dinitrogen starting material.
Tandem fixation: A highly efficient and versatile chemical cycle has been developed for the production of isocyanates through the molecular fixation of N2, CO2, and R3ECl (E=C, Si and Ge). Key steps include a simultaneous nitrene‐group transfer and oxygen‐atom transfer.