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DOI: 10.1055/s-0041-1737327
Elucidation of the Nucleophilic Potential of Diazocyclopentadiene
Financial support of this work by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie is gratefully acknowledged.
Dedicated to Professor Alain Krief on the occasion of his 80th birthday
Abstract
Diazocyclopentadiene reacts with benzhydrylium ions (Ar2CH+) to give 2,5-dibenzhydryl-substituted diazocyclopentadienes. The kinetics have been determined photometrically in dichloromethane under pseudo-first-order conditions using diazocyclopentadiene in excess. Plots of the second-order rate constants (log k 2) versus the electrophilicity parameters E of the benzhydrylium ions gave the nucleophilicity parameter N = 4.84 and susceptibility s N = 1.06 for diazocyclopentadiene according to the correlation log k(20 °C) = s N(E + N). Diazocyclopentadiene thus has a similar nucleophilic reactivity as pyrrole. Previously reported electrophilic substitutions of diazocyclopentadiene are rationalized by these parameters and new reaction possibilities are predicted.
Key words
diazo compounds - kinetics - linear free energy relationships - nucleophilicity - reactivity scalesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0041-1737327.
- Supporting Information
Publication History
Received: 12 November 2021
Accepted: 17 November 2021
Article published online:
05 January 2022
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