Details

Autor(en) / Beteiligte

• Keane, Andrew J.
• Farrell, Wesley S.
• Yonke, Brendan L.
• Zavalij, Peter Y.
• Sita, Lawrence R.

Titel

Metal-Mediated Production of Isocyanates, R3ENCO 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

Link zum Volltext

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 NN 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.