The role of odd-electron intermediates and in-cage electron transfer in ultrafast photochemical disproportionation reactions in Lewis bases.
Femtosecond visible pump-IR probe studies of Cp2W2(CO)6 in P(OMe)3 and CH2Cl2 have allowed direct observation of a 19-electron intermediate and of disproportionation into CpW(CO)3- and CpW(CO)3P(OMe)3+ on the ultrafast time scale. A new disproportionation mechanism involving in-cage electron transfer between a 19-electron intermediate and a 17-electron radical has been proposed.
Kling
Matthias F
MF
Department of Chemistry, University of California, Berkeley, CA 94720, USA.
Cahoon
James F
JF
Glascoe
Elizabeth A
EA
Shanoski
Jennifer E
JE
Harris
Charles B
CB