Catalytic reduction of dinitrogen to ammonia at a single molybdenum center.
Dinitrogen (N2) was reduced to ammonia at room temperature and 1 atmosphere with molybdenum catalysts that contain tetradentate [HIPTN3N]3- triamidoamine ligands (such as [HIPTN3N]Mo(N2), where [HIPTN3N]3- is [(3,5-(2,4,6-i-Pr3C6H2)2C6H3NCH2CH2)3N]3-) in heptane. Slow addition of the proton source [(2,6-lutidinium)(BAr'4), where Ar' is 3,5-(CF3)2C6H3]and reductant (decamethyl chromocene) was critical for achieving high efficiency ( approximately 66% in four turnovers). Numerous x-ray studies, along with isolation and characterization of six proposed intermediates in the catalytic reaction under noncatalytic conditions, suggest that N2 was reduced at a sterically protected, single molybdenum center that cycled from Mo(III) through Mo(VI) states.
Yandulov
Dmitry V
DV
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
Schrock
Richard R
RR
D000641:Ammonia / Q000737:chemistry*; D001274:Atmospheric Pressure; D002384:Catalysis; D002857:Chromium / Q000737:chemistry; D004583:Electrons; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008982:Molybdenum / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry*; D009591:Nitrogenase / Q000378:metabolism; D009942:Organometallic Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D011522:Protons; D013696:Temperature
D008024:Ligands; D009942:Organometallic Compounds; D011522:Protons; D002857:Chromium; D000641:Ammonia; D008982:Molybdenum; D009591:Nitrogenase; D009584:Nitrogen