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Metal‐Mediated Production of Isocyanates, R 3 ENCO from Dinitrogen, Carbon Dioxide, and R 3 ECl
Author(s) -
Keane Andrew J.,
Farrell Wesley S.,
Yonke Brendan L.,
Zavalij Peter Y.,
Sita Lawrence R.
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201502293
Subject(s) - chemistry , nitrene , isocyanate , metal , bond cleavage , polymer chemistry , photochemistry , organic chemistry , catalysis , polyurethane
A highly efficient and versatile chemical cycle has been developed for the production of isocyanates through the molecular fixation of N 2 , CO 2 and R 3 ECl (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 R 3 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 R 3 ECl regenerates a metal dichloride that is the precursor for dinuclear dinitrogen starting material.