Spectroscopic evidence for a new type of bonding between a thioether radical cation and a phenyl group.
The oxidation potential of thioethers constrained to be near aromatic rings is lowered, due to an antibonding interaction between the p-type sulfur lone pair with the neighboring phenyl π-system which on removal of an electron becomes a new kind of 3-electron S∴π bonding that reveals itself in the photoelectron spectrum and by an electronic transition involving the orbitals participating in the S∴π bond.
Department of Chemistry, University of Fribourg , CH-1700, Fribourg, Switzerland, and the Department of Chemistry and Biochemistry, The University of Arizona , Tucson, Arizona 85721, United States.
Nicolas P-A
NP
Monney
Thomas
T
Bally
Ganga S
GS
Bhagavathy
Richard S
RS
Glass
D002412:Cations / Q000737:chemistry*; D004583:Electrons; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013440:Sulfides / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*
D002412:Cations; D013440:Sulfides; D013455:Sulfur