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Kinetics and Mechanisms of Aryldiazonium Ions in Aqueous Solutions

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Aryl Diazonium Salts and Related Compounds

Part of the book series: Physical Chemistry in Action ((PCIA))

Abstract

In aqueous acid solution and in mixed alcohol-water solvents ([H3O+] > 10–2 M), in the dark and in the absence of reductants, the spontaneous decomposition of aryldiazonium, ArN2+, salts proceeds through borderline SN1 (DN + AN) -SN2 mechanisms. The rate constant values depend strongly on the nature of the substituents attached to the aromatic ring of ArN2+ and, for those with electron-withdrawing substituents, on solution composition. The product distribution is proportional to the composition of the solvation shell of the ipso carbon, which reflects the composition of the water/cosolvent mixture. However, upon decreasing moderately the acidity, reactions involving the formation of diazohydroxides, ArN2OH, diazoethers, ArN2OR, and diazoates, ArN2O−, become competitive and may even be the main decomposition pathway. The stability of ArN2OH, ArN2OR, and ArN2O− species (which may coexist with ArN2+ in solution) is intimately related to the Z-E (syn-anti, cis-trans) isomerization of the O-adducts, so that they may undergo further reactions when they are components of a Lewis acid-base equilibrium, or undergo homolytic scission to produce homolytic reduction products. In this book chapter, we aim to provide the reader with a practical and (hopefully) useful view of the complex chemistry of ArN2+ in aqueous and mixed alcohol-water solutions, mainly covering the kinetics and mechanisms of the reactions. In a last section, we introduce some analytical methods for the determination of diazonium salts and their degradation products.

Dedicated to Prof. Laurence S. Romsted (Rutgers, the State University of New Jersey, USA) for introducing us to the very complex—yet fascinating—chemistry of aryldiazonium ions, for his continuous support, encouragement, extremely fruitful discussions, and, most importantly, for his friendship.

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Acknowledgments

This book chapter was prepared during a sabbatical leave of CBD supported by the University of Vigo. We thank all colleagues for helpful discussions and, especially, to all students who participated with enthusiasm for years in the aryldiazonium project, making important contributions to this work. Financial support from Ministerio de Ciencia e Innovación (Spain), Xunta de Galicia and Universidad de Vigo is also acknowledged.

Credit authorship contribution statement.

C. B-D. Sections 1–3 and 5: conceptualization, visualization, writing, review & editing.

E. G-R. Section 4: conceptualization, visualization, writing, review & editing.

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Authors and Affiliations

  1. Physical Chemsitry Department, Universidad de Vigo, Vigo, Spain

    Carlos Bravo-Díaz

  2. Analytical and Food Chemistry Department, Universidad de Vigo, Vigo, Spain

    Elisa González-Romero

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  1. Carlos Bravo-Díaz
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  2. Elisa González-Romero
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Correspondence to Carlos Bravo-Díaz .

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Editors and Affiliations

  1. Université Paris Cité, CNRS, ITODYS, Paris, France

    Mohamed M. Chehimi

  2. Université Paris Cité, CNRS, ITODYS, Paris, France

    Jean Pinson

  3. Faculté des Sciences, LPCM, Mouloud Mammeri University of Tizi-Ouzou, Tizi-Ouzou, Algeria

    Fatima Mousli

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Bravo-Díaz, C., González-Romero, E. (2022). Kinetics and Mechanisms of Aryldiazonium Ions in Aqueous Solutions. In: Chehimi, M.M., Pinson, J., Mousli, F. (eds) Aryl Diazonium Salts and Related Compounds. Physical Chemistry in Action. Springer, Cham. https://doi.org/10.1007/978-3-031-04398-7_3

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