title: Bond-coupled electron transfer processes: cleavage of Si-Si bonds in disilanes.
abstract: Photooxidation of 1,1,2,2-tetra-tert-butyl-1,2-diphenyldisilane, 1, by triplet sensitizers in CHCl3/CCl4 solutions yields chlorosilane, 2, in high chemical yield. The quantum yield for formation of 2 depends on the energy of the ion radical pair formed following initial electron transfer. Dissociative return electron transfer (DRET) is proposed as the mechanism for the highly efficient Si-Si bond cleavage in 1. DRET may be a useful strategy for the fragmentation of other such bonds in di-, oligo-, and polysilanes as well as other group 4A compounds using a variety of sensitizers with different spectral properties.
authors.affiliation: Department of Chemistry, University of Rochester, Rochester, NY 14627, USA.
authors.forename: Rabih O
authors.initials: RO
authors.lastname: Al-Kaysi
authors.forename: Joshua L
authors.initials: JL
authors.lastname: Goodman