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Title: Dinitrogen Binding and Functionalization

Other · · Comprehensive Organometallic Chemistry IV
 [1];  [1];  [1];  [1]
  1. Yale Univ., New Haven, CT (United States)
+ Show Author Affiliations

This chapter presents fundamental aspects of the coordination chemistry of N2, including structure, spectroscopy, reactivity, and catalysis. We start by comparing and contrasting the binding of N2 with the isoelectronic CO ligand that is familiar to organometallic chemists, and show that though they are isolobal, there are significant differences. We also describe the numerous practical considerations to bear in mind when preparing, studying, and interpreting the properties and reactions of N2 complexes, and include pitfalls from the perspective of practitioners. The different binding modes and reactions of N2 complexes are tabulated, giving representative examples of various complexes and reactions. Formation of new bonds between N2 and H sources such as protons and H2, as well as multiatomic groups containing Si, C, and B, give insight into the status of the field and opportunities for the future.

Research Organization:
Yale Univ., New Haven, CT (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
DOE Contract Number:
SC0020315; DGE1752134
OSTI ID:
1903359
Journal Information:
Comprehensive Organometallic Chemistry IV, Vol. 1; Related Information: 2. Weber, J. E.; Bhutto, S. M.; Genoux, A. T.-Y.; Holland, P. L. "Dinitrogen Binding and Functionalization," in Comprehensive Organometallic Chemistry IV (Parkin, G.; Meyer, K.; O'Hare, D., eds.), Kidlington, UK, Elsevier, 2022, Vol. 1, pp. 521-554.
Country of Publication:
United States
Language:
English

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The Cambridge Structural Database
  • Groom, Colin R.; Bruno, Ian J.; Lightfoot, Matthew P.
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 2, p. 171-179 https://doi.org/10.1107/S2052520616003954
journal April 2016
Carbon−Nitrogen Bond Formation via the Reaction of Terminal Alkynes with a Dinuclear Side-on Dinitrogen Complex journal August 2004
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The importance of cyclopentadienyl substituent effects in group 4 metallocene dinitrogen chemistry journal April 2005
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Redox-Induced N2Hapticity Switching in Zirconocene Dinitrogen Complexes journal April 2013
Dinitrogen Binding and Cleavage by Multinuclear Iron Complexes journal June 2015
Recent Developments in Nitrogen Reduction Catalysts: A Virtual Issue journal December 2018
Nitrogen Atom Transfer from a Dinitrogen-Derived Vanadium Nitride Complex to Carbon Monoxide and Isocyanide journal November 2014
Reduction of dinitrogen bound at an iron(0) centre journal January 1996
Chemistry of ruthenium(II) and osmium(II) ammines journal January 1979
Azaferrocene-Based PNP-Type Pincer Ligand: Synthesis of Molybdenum, Chromium, and Iron Complexes and Reactivity toward Nitrogen Fixation: Azaferrocene-Based PNP-Type Pincer Ligand: Synthesis of Molybdenum, Chromium, and Iron Complexes and Reactivity toward Nitrogen Fixation journal September 2016
A picolinate-N2 complex of rhenium, the first dinitrogen complex bearing a carboxylate or a N,O-ligand journal September 2006
N–H Bond Dissociation Enthalpies and Facile H Atom Transfers for Early Intermediates of Fe–N 2 and Fe–CN Reductions journal February 2017
Nitrogen fixation in solution journal October 1995
Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen journal January 2014
Recent developments in synthetic nitrogen fixation journal January 2012
Use of Calix[4]arenes in the Redox Chemistry of Lanthanides:  the Reduction of Dinitrogen by a Calix[4]arene−Samarium Complex journal June 2007
Reactivity of Dinitrogen Bound to Mid- and Late-Transition-Metal Centers: Dinitrogen Bound to Mid- and Late-Transition Metal Centers journal January 2015
Improving the Reliability and Accuracy of Ammonia Quantification in Electro‐ and Photochemical Synthesis journal October 2019
Formation of Phosphorus−Nitrogen Bonds by Reduction of a Titanium Phosphine Complex under Molecular Nitrogen journal September 2005
Fine-Tuning the Energy Barrier for Metal-Mediated Dinitrogen N≡N Bond Cleavage journal July 2014
Nitrogen reduction and functionalization by a multimetallic uranium nitride complex journal July 2017
Tetrametallic Reduction of Dinitrogen: Formation of a Tetranuclear Samarium Dinitrogen Complex journal December 1999
Stepwise Reduction of Dinitrogen Bond Order by a Low-Coordinate Iron Complex
  • Smith, Jeremy M.; Lachicotte, Rene J.; Pittard, Karl A.
  • Journal of the American Chemical Society, Vol. 123, Issue 37, p. 9222-9223 https://doi.org/10.1021/ja016094+
journal August 2001
Photochemical Activation of the N≡N Bond in a Dimolybdenum-Dinitrogen Complex: Formation of a Molybdenum Nitride journal October 2001
Hydroboration of Coordinated Dinitrogen: A New Reaction for the N2 Ligand that Results in Its Functionalization and Cleavage journal October 2002

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nitrogen complexes
diazene
hydrazine
ammonia
proton-coupled electron transfer