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Determining and Understanding N-H Bond Strengths in Synthetic Nitrogen Fixation Cycles

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Nitrogen Fixation

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 60))

Abstract

The fixation of atmospheric dinitrogen to ammonia using molecular catalysts has been a long-standing challenge in homogeneous catalysis and synthetic chemistry. New approaches to this problem may offer more energy-efficient and carbon-neutral routes to this important industrial compound. Despite the ubiquity of ammine, amide, imide and diazenide ligands in coordination chemistry, little thermodynamic data is available for understanding N-H bond strengths in molecules bearing these nitrogenous fragments. This article presents an overview of both computational and experimental approaches for the determination of N-H bond dissociation free energies in a variety of compounds relevant to nitrogen fixation to ammonia. The influence of metal oxidation state, ancillary ligand and identity of the nitrogen donor are highlighted. Implications for future design of molecular systems for the reduction of dinitrogen are discussed.

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Authors and Affiliations

  1. Department of Chemistry, Princeton University, Princeton, NJ, 08544, USA

    Máté J. Bezdek, Iraklis Pappas & Paul J. Chirik

Authors
  1. Máté J. Bezdek
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  2. Iraklis Pappas
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  3. Paul J. Chirik
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Corresponding author

Correspondence to Paul J. Chirik .

Editor information

Editors and Affiliations

  1. The University of Tokyo, Department of Systems Innovation, School of Engineering, Hongo, Tokyo, Japan

    Yoshiaki Nishibayashi

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Bezdek, M.J., Pappas, I., Chirik, P.J. (2017). Determining and Understanding N-H Bond Strengths in Synthetic Nitrogen Fixation Cycles. In: Nishibayashi, Y. (eds) Nitrogen Fixation. Topics in Organometallic Chemistry, vol 60. Springer, Cham. https://doi.org/10.1007/3418_2016_8

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