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Direct conversion of dinitrogen (N2) into organic compounds, not through ammonia (NH3), is of great significance both fundamentally and practically. Here, we report a scandium-mediated high-efficient synthetic cycle affording hydrazine derivatives (RMeN-NMeR') directly from N2 molecule and carbon-based electrophiles. The cycle includes three main steps: i) reduction of halogen-bridged discandium complex under N2 leading to (N2)3--bridged discandium complex via (N2)2- intermediate, ii) treatment of the (N2)3- complex with methyl triflate (MeOTf) affording (N2Me2)2--bridged discandium complex, and iii) further reaction of the (N2Me2)2- complex with carbon-based electrophiles producing hydrazine derivatives along with regeneration of the halide precursor. Furthermore, insertion of a CO molecule into one Sc-N bond in the (N2Me2)2--scandium complex was observed. Most notably, this is the first example of rare-earth metal-promoted direct conversion of N2 to organic compounds; the formation of C-N bonds by the reaction of these (N2)3- and (N2Me2)2- complexes with electrophiles represents the first case among all N2-metal complexes reported.
PMID: 31117668 [PubMed - as supplied by publisher]