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Metal-Mediated Production of Isocyanates, R3 EN=C=O from Dinitrogen, Carbon Dioxide, and R3 ECl.

著者 Keane AJ , Farrell WS , Yonke BL , Zavalij PY , Sita LR
Angew Chem Int Ed Engl.2015 Aug 24 ; 54(35):10220-4.
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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.
PMID: 26118362 [PubMed]
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