The Mechanism of Hydrolysis of Aryldiazonium Ions Revisited: Marcus Theory vs. Canonical Variational Transition State Theory

• Published in: European journal of organic chemistry 2013-09, Vol.2013 (27), p.6098-6107
• Main Authors: García Martínez, Antonio, de la Moya Cerero, Santiago, Osío Barcina, José, Moreno Jiménez, Florencio, Lora Maroto, Beatriz
• Format: Article
• Language: English
• Subjects: Biophysics; Cations; Density functional calculations; Hydrolysis; Nucleophilic substitution; Reaction mechanisms; Theory
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201300834

Several models, theoretical levels and computational methods, all based on the canonical variational transition state approximation, have been used to predict both the experimental activation energies (ΔEexp≠) and the experimental activation free energies (ΔGexp≠) for the hydrolysis of aryldiazonium ions. It is demonstrated that the computation of activation energies (ΔE≠), instead of activation free energies (ΔG≠), agrees better with the corresponding experimental data, showing that the employed computational methods do not afford reliable entropic contributions to the free energy barriers in the case of the studied reaction. However, the most fitted computations of ΔE≠ were not able to clearly differentiate between the mechanisms proposed for this interesting reaction (SN1, SN2 and water cluster). In contrast, the use of the Marcus theory (hyperbolic‐cosine equation) instead of the canonical variational transition state theory leads to excellent agreement between the in‐water‐computed activation energies (ΔEwM≠) and the corresponding ΔEexp≠ values for the SN2 mechanism, but far beyond the limit of error for the SN1 process. The validity of the Marcus theory for the studied SN1 and SN2 reactions is ensured by the fact that both reactions can be described as SET processes. On the other hand, apparently compelling evidence against the SN2 mechanism, such as 13C KIEs and experimental observation of N2 scrambling, are also discussed and alternative explanations are proposed. The controversial mechanism for the hydrolysis of aryldiazonium ions is computationally studied on the basis of different models, levels and methods. Only Marcus Theory, instead of variational transition state theory, in combination with simple DFT calculations is able to predict the experimental barriers when the SN2 mechanism is taken into account, supporting such mechanism over others.