Reversible dimerization of anion radicals of carbonyl compounds and the electrosynthesis of pinacols. The case of 9-fluorenone

Reversible dimerization of anion radicals of carbonyl compounds and the electrosynthesis of pinacols. The case of 9-fluorenone Full article

Journal

Electrochimica Acta
ISSN: 1873-3859 , E-ISSN: 0013-4686

Output data

Year: 2020, Volume: 358, Article number : 136903, Pages count : DOI: 10.1016/j.electacta.2020.136903

Authors

Mendkovich Andrey S. ¹ , Ngom Arona ^2,3 , Kokorekin Vladimir A. ¹ , Mikhailov Mikhail N. ¹ , Gningue-Sall Diariatou ² , Jouikov Viatcheslav ³

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation
2	LCPOAI, Chemistry department, University Cheikh Anta DIOP of Dakar, BP5005 Dakar, Senegal
3	UMR 6226 - ISCR, University of Rennes 1, 35042 Rennes, France

Reversible dimerization of the anion radicals of carbonyl compounds was studied by cyclic voltammetry, chronoamperometry, electrolysis, digital simulation and quantum chemical calculations using electroreduction of 9-fluorenone in DMF/0.1 M Bu4NClO4 as an example. The experimental data confirmed that this reaction is thermodynamically unfavorable as it was predicted by DFT calculations. In contrast with some other anion radicals, neither ion pairing of 9-fluorenone anion radicals with lithium cation nor their hydrogen bonding with water shifts the dimerization equilibrium to the dimeric product. Reversibility of the dimerization decreases in the presence of phenol due to the protonation of the dimeric dianion and to the irreversibility of dimerization of the anion radical – phenol complexes. The contribution of these two pathways to general hydrodimerization process is discussed.

Mendkovich A.S. , Ngom A. , Kokorekin V.A. , Mikhailov M.N. , Gningue-Sall D. , Jouikov V.
Reversible dimerization of anion radicals of carbonyl compounds and the electrosynthesis of pinacols. The case of 9-fluorenone
Electrochimica Acta. 2020. V.358. 136903 . DOI: 10.1016/j.electacta.2020.136903 WOS Scopus OpenAlex

Web of science:	WOS:000575852100002
Scopus:	2-s2.0-85089495450
OpenAlex:	W3048364725

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