G. Eckert et M. Goez, CIDNP investigation of radical decay pathways in the sensitized photolysisof triphenylsulfonium salts, J AM CHEM S, 121(10), 1999, pp. 2274-2280
The photodecomposition of triphenylsulfonium hexafluoroantimonate was studi
ed by pseudo-steady-state and time-resolved CIDNP experiments, using naphth
alene and 9,10-dimethylanthracene as (singlet) sensitizers. Key intermediat
es of these reactions are radical pairs consisting of the sensitizer radica
l cation Sens(.+) and the phenyl radical Ph-., which are formed by photoind
uced electron transfer followed by cleavage of the resulting neutral onium
radical. The chemical fate of Ph-. is strongly influenced by the sensitizer
. With 9, 10-dimethylanthracene, in-cage hydrogen abstraction from the meth
yl groups of Sens(.+) produces benzene and a carbocation that can function
as a protic acid; free radicals Ph-. attack surplus sensitizer to give addi
tion products. With naphthalene, geminate combination of the two radicals a
nd in-cage oxidation of diphenyl sulfide (the by-product of cleavage of the
onium radical) by Sens(.+) are observed. In both Systems, the solvent scav
enges free Ph-., yielding monodeuteriobenzene. The rate constant of this re
action was determined to be 1.2 x 10(4) M-1 s(-1) at 241 K. With 9,10-dimet
hylanthracene, the competition of sensitizer and solvent for the free radic
als Ph-. was studied quantitatively by evaluating the lineshape of the supe
rimposed CIDNP signals of undeuterated and monodeuterated benzene. By a sim
ple kinetic model the dependence of the product distribution on temperature
and sensitizer concentration could be described with a consistent set of p
arameters.