Dinitrogen cleavage and functionalization by carbon monoxide promoted by a hafnium complex.
Molecular nitrogen (N(2)) and carbon monoxide (CO) have the two strongest bonds in chemistry and present significant challenges in developing new transformations that exploit these two abundant feedstocks. At the core of this objective is the discovery of transition-metal compounds that promote the six-electron reductive cleavage of N(2) at ambient temperature and pressure and also promote new nitrogen-element bond formation. Here we show that an organometallic hafnium compound induces N(2) cleavage on the addition of CO, with a simultaneous assembly of new nitrogen-carbon and carbon-carbon bonds. Subsequent addition of a weak acid liberates oxamide, which demonstrates that an important agrochemical can be synthesized directly from N(2) and CO. These studies introduce an alternative paradigm for N(2) cleavage and functionalization in which the six-electron reductive cleavage is promoted by both the transition metal and the incoming ligand, CO, used for the new bond formations.
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, USA.
Donald J
DJ
Knobloch
Emil
E
Lobkovsky
Paul J
PJ
Chirik
D002248:Carbon Monoxide / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006195:Hafnium / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D009584:Nitrogen / Q000737:chemistry*; D013237:Stereoisomerism
D056831:Coordination Complexes; D002248:Carbon Monoxide; D009584:Nitrogen; D006195:Hafnium