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Dinitrogen Binding and Functionalization

Other · · Comprehensive Organometallic Chemistry IV
 [1];  [2];  [2];  [2]
  1. Yale Univ., New Haven, CT (United States); Yale University
  2. 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;
Other Award/Contract Number:
DGE1752134
OSTI ID:
1903359
Country of Publication:
United States
Language:
English

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  • 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
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Direct transformation of dinitrogen: synthesis of N-containing organic compounds via N−C bond formation journal June 2020
False detail in three-dimensional Fourier representations of crystal structures journal July 1948
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
N2 Reduction and Hydrogenation to Ammonia by a Molecular Iron-Potassium Complex journal November 2011
Radical SAM-Dependent Carbon Insertion into the Nitrogenase M-Cluster journal September 2012
Dinitrogen Cleavage by a Three-Coordinate Molybdenum(III) Complex journal May 1995
Transformation of Coordinated Dinitrogen by Reaction with Dihydrogen and Primary Silanes journal March 1997
Dinitrogen Bridged Gold Clusters journal March 1997
Bimetallic System for Nitrogen Fixation: Ruthenium-Assisted Protonation of Coordinated N2 on Tungsten with H2 journal January 1998
Coordination-induced weakening of ammonia, water, and hydrazine X–H bonds in a molybdenum complex journal November 2016
Nitrogen fixation and reduction at boron journal February 2018
Terminal coordination of diatomic boron monofluoride to iron journal March 2019
Dinitrogen complexation and reduction at low-valent calcium journal March 2021
Functionalization and cleavage of coordinated dinitrogen via hydroboration using primary and secondary boranes journal April 2005
The importance of cyclopentadienyl substituent effects in group 4 metallocene dinitrogen chemistry journal April 2005
Catalytic Nitrogen Fixation via Direct Cleavage of Nitrogen–Nitrogen Triple Bond of Molecular Dinitrogen under Ambient Reaction Conditions journal October 2017
Reactions of Ligating Dinitrogen with Alcohols or Metal Hydrides journal June 1980
Novel Disilylation and Germylation of Coordinated Dinitrogen in cis -[W(N 2 ) 2 (PMe 2 Ph) 4 ] journal August 1990
Synthesis of Boryldiazenido Complexes from Tungsten Dinitrogen Complexes journal July 1998
Iridium-catalyzed Formation of Silylamine from Dinitrogen under Ambient Reaction Conditions journal July 2020
Chemistry of ruthenium(II) and osmium(II) ammines journal January 1979
The Contamination of Commercial 15N2 Gas Stocks with 15N–Labeled Nitrate and Ammonium and Consequences for Nitrogen Fixation Measurements journal October 2014
Dinitrogen and Related Chemistry of the Lanthanides: A Review of the Reductive Capture of Dinitrogen, As Well As Mono- and Di-aza Containing Ligand Chemistry of Relevance to Known and Postulated Metal Mediated Dinitrogen Derivatives journal February 2010

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ammonia
diazene
hydrazine
nitrogen complexes
proton-coupled electron transfer