The role of odd-electron intermediates and in-cage electron transfer in ultrafast photochemical disproportionation reactions in Lewis bases

Matthias F Kling; James F Cahoon; Elizabeth A Glascoe; Jennifer E Shanoski; Charles B Harris

doi:10.1021/ja046223x

The role of odd-electron intermediates and in-cage electron transfer in ultrafast photochemical disproportionation reactions in Lewis bases

J Am Chem Soc. 2004 Sep 22;126(37):11414-5. doi: 10.1021/ja046223x.

Authors

Matthias F Kling¹, James F Cahoon, Elizabeth A Glascoe, Jennifer E Shanoski, Charles B Harris

Affiliation

¹ Department of Chemistry, University of California, Berkeley, CA 94720, USA.

PMID: 15366868
DOI: 10.1021/ja046223x

Abstract

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.