Catalytic reduction of dinitrogen to ammonia at a single molybdenum center.
This account explores the catalytic reduction of dinitrogen by molybdenum complexes that contain the [HIPTN(3)N](3-) ligand ([HIPTN(3)N](3-)) = [(HIPTNCH(2)CH(2))(3)N](3-), where HIPT = 3,5-(2,4,6-i-Pr(3)C(6)H(2))(2)C(6)H3) at room temperature and pressure with protons and electrons. A total of 7-8 equiv of ammonia is formed out of approximately 12 possible (depending upon the Mo derivative employed). No hydrazine is formed. Numerous X-ray studies of proposed intermediates in the catalytic cycle suggest that N(2) is being reduced at a sterically protected, single Mo center operating in oxidation states between Mo(III) and Mo(VI). Subtle variations of the [HIPTN(3)N](3-) ligand are not as successful as a consequence of an unknown shunt in the catalytic cycle that consumes reduction equivalents to yield (it is proposed) dihydrogen [corrected]
Schrock
Richard R
RR
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, 02139, USA. rrs@mit.edu
D000641:Ammonia / Q000737:chemistry*; D002384:Catalysis; D008982:Molybdenum / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry*; D010084:Oxidation-Reduction
D000641:Ammonia; D008982:Molybdenum; D009584:Nitrogen