Selenium–Selenium Bond Cleavage of Diaryl Diselenide Radical Anions During Pulse Radiolysis. Issue 1 (24th October 2014)

• Record Type: Journal Article
• Authors: Tojo, Sachiko; Fujitsuka, Mamoru; Ouchi, Akihiko; Majima, Tetsuro
• Is Part Of: ChemPlusChem. Volume 80:Issue 1(2015:Jan.)
• Page Start: 68
• Page End: 73
• Publication Date: 2014-10-24
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1002/cplu.201402300
• Languages: English
• ISSNs: 2192-6506

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>A seleniumselenium σ‐bond (SeSe) cleavage of a diaryl diselenide radical anion (ArSeSeAr<bold>^.</bold>⁻) was investigated by absorption measurements during the γ radiolysis and pulse radiolysis in 2‐methyltetrahydrofuran. A di‐α‐naphthyl diselenide radical anion (^αNpSeSe^αNp<bold>^.</bold>⁻) in which an unpaired electron is localized in the SeSe σ* orbital between both Se atoms with an elongated SeSe bond showed an absorption band at 440 nm at 77 K. Upon increasing temperature, the absorption band at 440 nm shifted to 540 nm, thus suggesting that an unpaired electron is delocalized over two naphthalene rings and the SeSe bond. The disappearance of the absorption band at 540 nm and formation of absorption bands at 420, 620, and 690 nm assigned to the α‐naphthylselenyl radical were observed during the pulse radiolysis of ^αNpSeSe^αNp, thus indicating that the SeSe bond cleavage occurred in ^αNpSeSe^αNp<bold>^.</bold>⁻. The relationship between the SeSe bond cleavage and delocalization of the unpaired electron in ArSeSeAr<bold>^.</bold>⁻ is discussed.</p> </abstract>