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Competition Between Cα‐S and Cα‐Cβ Bond Cleavage in β‐Hydroxysulfoxides Cation Radicals Generated by Photoinduced Electron Transfer†.

Authors :
Lapi, Andrea
D'Alfonso, Claudio
Del Giacco, Tiziana
Lanzalunga, Osvaldo
Source :
Photochemistry & Photobiology; Nov/Dec2021, Vol. 97 Issue 6, p1310-1321, 12p
Publication Year :
2021

Abstract

A kinetic and product study of the 3‐cyano‐N‐methyl‐quinolinium photoinduced monoelectronic oxidation of a series of β‐hydroxysulfoxides has been carried out to investigate the competition between Cα‐S and Cα‐Cβ bond cleavage within the corresponding cation radicals. Laser flash photolysis experiments unequivocally established the formation of sulfoxide cation radicals showing their absorption band (λmax ≈ 520 nm) and that of 3‐CN‐NMQ• (λmax ≈ 390 nm). Steady‐state photolysis experiments suggest that, in contrast to what previously observed for alkyl phenyl sulfoxide cation radicals that exclusively undergo Cα‐S bond cleavage, the presence of a β‐hydroxy group makes, in some cases, the Cα‐Cβ scission competitive. The factors governing this competition seem to depend on the relative stability of the fragments formed from the two bond scissions. Substitution of the β‐OH group with ‐OMe did not dramatically change the reactivity pattern of the cation radicals thus suggesting that the observed favorable effect of the hydroxy group on the Cα‐Cβ bond cleavage mainly resides on its capability to stabilize the carbocation formed upon this scission. [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
00318655
Volume :
97
Issue :
6
Database :
Complementary Index
Journal :
Photochemistry & Photobiology
Publication Type :
Academic Journal
Accession number :
154222475
Full Text :
https://doi.org/10.1111/php.13455