Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen.

Dinitrogen cleavage and hydrogenation by transition-metal centers to produce ammonia is central in industry and in Nature. After an introductory section on the thermodynamic and kinetic challenges linked to N2 splitting, this tutorial review discusses three major classes of transition-metal systems (homogeneous, heterogeneous and biological) capable of achieving dissociation and hydrogenation of dinitrogen. Molecular complexes, solid-state Haber-Bosch catalytic systems, silica-supported tantalum hydrides and nitrogenase will be discussed. Emphasis is focused on the reaction mechanisms operating in the process of dissociation and hydrogenation of dinitrogen, and in particular on the key role played by metal hydride bonds and by dihydrogen in such reactions.

[1]  Patrick L. Holland,et al.  Recent developments in the homogeneous reduction of dinitrogen by molybdenum and iron. , 2013, Nature chemistry.

[2]  Dawei Yang,et al.  Ammonia formation by a thiolate-bridged diiron amide complex as a nitrogenase mimic , 2013, Nature Chemistry.

[3]  L. Seefeldt,et al.  Nitrogenase: a draft mechanism. , 2013, Accounts of chemical research.

[4]  Yilin Hu,et al.  Radical SAM-Dependent Carbon Insertion into the Nitrogenase M-Cluster , 2012, Science.

[5]  J. Mayer,et al.  Using combinations of oxidants and bases as PCET reactants: thermochemical and practical considerations , 2012 .

[6]  D. Nocera,et al.  Proton-coupled electron transfer kinetics for the hydrogen evolution reaction of hangman porphyrins , 2012 .

[7]  E. A. Quadrelli,et al.  Successive heterolytic cleavages of H2 achieve N2 splitting on silica-supported tantalum hydrides: a DFT proposed mechanism. , 2012, Inorganic chemistry.

[8]  L. Seefeldt,et al.  Unification of reaction pathway and kinetic scheme for N2 reduction catalyzed by nitrogenase , 2012, Proceedings of the National Academy of Sciences.

[9]  D. R. Tyler,et al.  Coordination of a complete series of N2 reduction intermediates (N2H2, N2H4, and NH3) to an iron phosphine scaffold. , 2012, Inorganic chemistry.

[10]  D. Rees,et al.  Evidence for Interstitial Carbon in Nitrogenase FeMo Cofactor , 2011, Science.

[11]  Frank Neese,et al.  X-ray Emission Spectroscopy Evidences a Central Carbon in the Nitrogenase Iron-Molybdenum Cofactor , 2011, Science.

[12]  E. A. Quadrelli,et al.  Heterolytic cleavage of ammonia N–H bond by bifunctional activation in silica-grafted single site Ta(V) imido amido surface complex. Importance of the outer sphere NH3 assistance , 2011 .

[13]  E. A. Quadrelli,et al.  Ammonia and Dinitrogen Activation by Surface Organometallic Chemistry on Silica‐Grafted Tantalum Hydrides , 2011 .

[14]  Y. Miyake,et al.  A molybdenum complex bearing PNP-type pincer ligands leads to the catalytic reduction of dinitrogen into ammonia. , 2011, Nature chemistry.

[15]  Gabor A. Somorjai,et al.  Impact of surface chemistry , 2010, Proceedings of the National Academy of Sciences.

[16]  Jonas C. Peters,et al.  Triggering N2 Uptake via Redox Induced Expulsion of Coordinated NH3 and N2 Silylation at Trigonal Bipyramidal Iron , 2010, Nature Chemistry.

[17]  M. D. Fryzuk,et al.  The hydride route to the preparation of dinitrogen complexes. , 2010, Chemical communications.

[18]  P. Chirik,et al.  Dinitrogen cleavage and functionalization by carbon monoxide promoted by a hafnium complex. , 2010, Nature chemistry.

[19]  J. Hartwig.  Organotransition Metal Chemistry: From Bonding to Catalysis , 2009 .

[20]  E. A. Quadrelli,et al.  H/D Exchange on Silica-Grafted Tantalum(V) Imido Amido [(≡SiO)2Ta(V)(NH)(NH2)] Synthesized from Either Ammonia or Dinitrogen: IR and DFT Evidence for Heterolytic Splitting of D2 , 2009 .

[21]  L. Seefeldt,et al.  Climbing nitrogenase: toward a mechanism of enzymatic nitrogen fixation. , 2009, Accounts of chemical research.

[22]  M. D. Fryzuk.  Side-on end-on bound dinitrogen: an activated bonding mode that facilitates functionalizing molecular nitrogen. , 2009, Accounts of chemical research.

[23]  Shuhua Li,et al.  Energetics and mechanism of dinitrogen cleavage at a mononuclear surface tantalum center: a new way of dinitrogen reduction. , 2008, Angewandte Chemie.

[24]  R. Schrock,et al.  Catalytic reduction of dinitrogen to ammonia by molybdenum: theory versus experiment. , 2008, Angewandte Chemie.

[25]  G. Ertl.  Reactions at surfaces: from atoms to complexity (Nobel Lecture). , 2008, Angewandte Chemie.

[26]  Barbara Kirchner,et al.  First-principles investigation of the Schrock mechanism of dinitrogen reduction employing the full HIPTN3N ligand. , 2008, Inorganic chemistry.

[27]  F. Studt,et al.  Energetics and mechanism of ammonia synthesis through the Chatt Cycle: conditions for a catalytic mode and comparison with the Schrock Cycle. , 2008, Chemistry.

[28]  T. Meyer,et al.  Proton-coupled electron transfer. , 2007, Chemical reviews.

[29]  G. Kubas,et al.  Fundamentals of H2 binding and reactivity on transition metals underlying hydrogenase function and H2 production and storage. , 2007, Chemical reviews.

[30]  E. A. Quadrelli,et al.  Dinitrogen Dissociation on an Isolated Surface Tantalum Atom , 2007, Science.

[31]  E. A. Quadrelli,et al.  Well-defined surface imido amido tantalum(v) species from ammonia and silica-supported tantalum hydrides. , 2007, Journal of the American Chemical Society.

[32]  N. Nakicenovic,et al.  Climate change 2007: Mitigation. Contribution of Working Group III to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change. Summary for Policymakers. , 2007 .

[33]  T. Wilbanks,et al.  Contribution of Working Group II to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change , 2007 .

[34]  H. Jónsson,et al.  Predicting catalysis: understanding ammonia synthesis from first-principles calculations. , 2006, The journal of physical chemistry. B.

[35]  F. Studt,et al.  Theoretical, spectroscopic, and mechanistic studies on transition‐metal dinitrogen complexes: Implications to reactivity and relevance to the nitrogenase problem , 2006, Journal of computational chemistry.

[36]  F. Studt,et al.  Energetics and mechanism of a room-temperature catalytic process for ammonia synthesis (Schrock cycle): comparison with biological nitrogen fixation. , 2005, Angewandte Chemie.

[37]  I. Dance.  The hydrogen chemistry of the FeMo-co active site of nitrogenase. , 2005, Journal of the American Chemical Society.

[38]  J. Nørskov,et al.  Ammonia Synthesis from First-Principles Calculations , 2005, Science.

[39]  D. Rees,et al.  Structural Basis of Biological Nitrogen Fixation. , 1996, Chemical reviews.

[40]  P. Chirik,et al.  Hydrogenation and cleavage of dinitrogen to ammonia with a zirconium complex , 2004, Nature.

[41]  A. Shilov,et al.  Catalytic reduction of molecular nitrogen in solutions , 2003 .

[42]  Michael P. Shaver,et al.  Activation of Molecular Nitrogen: Coordination, Cleavage and Functionalization of N2 Mediated by Metal Complexes , 2003 .

[43]  Richard R. Schrock,et al.  Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center , 2003, Science.

[44]  Robert Schlögl,et al.  Catalytic synthesis of ammonia-a "never-ending story"? , 2003, Angewandte Chemie.

[45]  Jeffrey A. Nichols,et al.  Ionization Potential, Electron Affinity, Electronegativity, Hardness, and Electron Excitation Energy: Molecular Properties from Density Functional Theory Orbital Energies , 2003 .

[46]  D. Rees,et al.  Nitrogenase MoFe-Protein at 1.16 Å Resolution: A Central Ligand in the FeMo-Cofactor , 2002, Science.

[47]  Y. Nishibayashi,et al.  Formation of ammonia in the reactions of a tungsten dinitrogen with ruthenium dihydrogen complexes under mild reaction conditions. , 2000, Inorganic chemistry.

[48]  S. Dahl,et al.  Surface science based microkinetic analysis of ammonia synthesis over ruthenium catalysts , 2000 .

[49]  P. Coppens,et al.  The First Crystallographic Evidence for Side-On Coordination of N2 to a Single Metal Center in a Photoinduced Metastable State , 2000 .

[50]  Vaclav Smil,et al.  Detonator of the population explosion , 1999, Nature.

[51]  Iwai,et al.  Bimetallic system for nitrogen fixation: ruthenium-assisted protonation of coordinated N2 on tungsten with H2 , 1998, Science.

[52]  C. Pickett.  The Chatt cycle and the mechanism of enzymic reduction of molecular nitrogen , 1996, JBIC Journal of Biological Inorganic Chemistry.

[53]  B. Burgess,et al.  Mechanism of Molybdenum Nitrogenase. , 1996, Chemical reviews.

[54]  G. J. Leigh,et al.  Reduction of dinitrogen bound at an iron(0) centre , 1996 .

[55]  C. Cummins,et al.  Dinitrogen Cleavage by a Three-Coordinate Molybdenum(III) Complex , 1995, Science.

[56]  G. J. Leigh.  Protonation of Coordinated Dinitrogen , 1992 .

[57]  S. Bare,et al.  The importance of C7 sites and surface roughness in the ammonia synthesis reaction over iron , 1987 .

[58]  R. Thorneley,et al.  The mechanism of Klebsiella pneumoniae nitrogenase action. Pre-steady-state kinetics of an enzyme-bound intermediate in N2 reduction and of NH3 formation. , 1984, The Biochemical journal.

[59]  J. Dilworth,et al.  Recent advances in the chemistry of nitrogen fixation , 1978 .