Bond-Coupled Electron Transfer Processes:  Cleavage of Si−Si Bonds in Disilanes

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. Dissociati...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2005-02, Vol.127 (6), p.1620-1621
Main Authors: Al-Kaysi, Rabih O, Goodman, Joshua L
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
General and physical chemistry
Photochemistry
Physical chemistry of induced reactions (with radiations, particles and ultrasonics)
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Summary: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.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja0432564