title: Metal-Mediated Production of Isocyanates, R3 EN=C=O from Dinitrogen, Carbon Dioxide, and R3 ECl.
abstract: 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.
authors.affiliation: Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742 (USA).
authors.forename: Andrew J
authors.initials: AJ
authors.lastname: Keane
authors.affiliation: Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742 (USA).
authors.forename: Wesley S
authors.initials: WS
authors.lastname: Farrell
authors.affiliation: Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742 (USA).
authors.forename: Brendan L
authors.initials: BL
authors.lastname: Yonke
authors.affiliation: Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742 (USA).
authors.forename: Peter Y
authors.initials: PY
authors.lastname: Zavalij
authors.affiliation: Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742 (USA). lsita@umd.edu.
authors.forename: Lawrence R
authors.initials: LR
authors.lastname: Sita
keywords: nitrene-group transfer; nitrogen fixation; oxygen-atom transfer; small-molecule activation