Resonance Raman spectra and structure of phenylthiyl radical

Time-resolved resonance Raman spectroscopy is used to compare the structures of the Phenythiyl Radical (PhS{sup {lg_bullet}}) and the Phenoxy (PhO) Radical. The C-S single bond of PhS{sup {lg_bullet}}, the unpaired electron on the sulfur, but the C=O double bond of PhO{sup {lg_bullet}} has a delocalized spin on the ring. PhS{sup {lg_bullet}} also has lower {upsilon}{sub 7a}, {upsilon}{sub 12}, and {upsilon}{sub 6a} frequencies than PhO {sup {lg_bullet}} - The large drop in {upsilon}{sub 7a} being due to drastically reduced C-S bond strength. The structural differences in the two radicals account for their different reactivities and absorption at the 400-510 nm region. 45 refs., 4 figs., 4 tabs.