Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center
Top Cited Papers
- 10 November 2005
- journal article
- research article
- Published by American Chemical Society (ACS) in Accounts of Chemical Research
- Vol. 38 (12) , 955-962
- https://doi.org/10.1021/ar0501121
Abstract
This Account explores the catalytic reduction of dinitrogen by molybdenum complexes that contain the [HIPTN3N]3- ligand ([HIPTN3N]3- = [(HIPTNCH2CH2)3N]3-, where HIPT = 3,5-(2,4,6-i-Pr3C6H2)2C6H3) at room temperature and pressure with protons and electrons. A total of 7−8 equiv of ammonia is formed out of ∼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 N2 is being reduced at a sterically protected, single Mo center operating in oxidation states between MoIII and MoVI. Subtle variations of the [HIPTN3N]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.Keywords
This publication has 30 references indexed in Scilit:
- Some Organometallic Chemistry of Molybdenum Complexes that Contain the [HIPTN3N]3- Triamidoamine Ligand, {[3,5-(2,4,6-i-Pr3C6H2)2C6H3NCH2CH2]3N}3-Organometallics, 2005
- Synthesis of tungsten complexes that contain hexaisopropylterphenyl-substituted triamidoamine ligands, and reactions relevant to the reduction of dinitrogen to ammoniaCanadian Journal of Chemistry, 2005
- Characterization of a Tungsten-Substituted Nitrogenase Isolated from Rhodobacter capsulatus,Biochemistry, 2003
- Synthesis of [(Me3SiNCH2CH2)3N]3- and [(C6F5NCH2CH2)3N]3- Complexes of Molybdenum and Tungsten That Contain CO, Isocyanides, or EthyleneOrganometallics, 2000
- Tungsten and Molybdenum Alkyl or Aryl Complexes That Contain the [(C6F5NCH2CH2)3N]3- LigandOrganometallics, 1998
- Synthesis and Decomposition of Alkyl Complexes of Molybdenum(IV) That Contain a [(Me3SiNCH2CH2)3N]3-Ligand. Direct Detection of α-Elimination Processes That Are More than Six Orders of Magnitude Faster than β-Elimination ProcessesJournal of the American Chemical Society, 1997
- In Quest of Competitive Catalysts for Nitrogenases and Other Metal Sulfur EnzymesAccounts of Chemical Research, 1997
- Structure−Function Relationships of Alternative NitrogenasesChemical Reviews, 1996
- Threshold Phenomena and Long-Distance Activation of Transcription by RNA Polymerase IIScience, 1992
- Dinitrogen complexes of the transition metalsChemical Reviews, 1973