Sonochemical synthesis of novel C60 fullerene 1,4-oxathiane derivative through the intermediate fullerene radical anion

Zemfira S Kinzyabaeva; Denis Sh Sabirov

doi:10.1016/j.ultsonch.2020.105169

Sonochemical synthesis of novel C₆₀ fullerene 1,4-oxathiane derivative through the intermediate fullerene radical anion

Ultrason Sonochem. 2020 Oct:67:105169. doi: 10.1016/j.ultsonch.2020.105169. Epub 2020 May 8.

Authors

Zemfira S Kinzyabaeva¹, Denis Sh Sabirov²

Affiliations

¹ Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, 141 Prospekt Oktyabrya, Ufa 450075, Russia. Electronic address: zefa5@rambler.ru.
² Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, 141 Prospekt Oktyabrya, Ufa 450075, Russia.

PMID: 32417624
DOI: 10.1016/j.ultsonch.2020.105169

Abstract

We have discovered a selective and efficient method for the synthesis of previously unknown 1,9-(1',4'-oxathiano)-1,9-dihydro-(C₆₀-I_h)[5,6]fullerene, a compound with the direct attachment of the sulfur atom to the fullerene core. The method is based on the reaction of C₆₀ with 1,2-hydroxythiols in the presence of inorganic bases in air under ultrasonication. The significance of ultrasound has been exemplified with the comparative conventional methods. The title compound has been identified with mass-(MALDI TOF/TOF), one- and two-dimensional NMR ¹H and ¹³C (COSY, HSQC, HMBS), IR, UV-Vis spectroscopic techniques. Using the direct EPR method, we have detected radical anion C₆₀^- (g = 2.0046 and ΔH = 2 G) as a key reaction intermediate of the sonochemical reaction. Based on the experimental results and quantum chemical calculations, we have proposed a mechanism for the conversion of C₆₀ and 2-mercaptoethanol to the C₆₀-1,4-oxathiane adduct.

Keywords: 1,4-Oxathiane; Cycloaddition reaction; EPR; Fullerene C(60); Radical anion of C(60); Ultrasound.