Peter Trefonas, James R. Damewood, et al.
Organometallics
Photolysis of the high polymer (n-C6H13, MeSi)nin CCL4leads to the formation of C2CL6, indicating that the photodegradative pathway of these polymers includes the formation of silyl radicals. Photolysis of alkyl-substituted polysilane polymers, (R1R2Si)n (R1= n-hexyl, R2 = Me; R1 = R2 = n-hexyl; R1= cyclohexyl, R2 = Me), at 254 nm in the presence of triethylsilane gives two major products, Et3Si-R1R2SiH and HR1R2Si-R1R2SiH. Photolysis of (n-C6H13MeSi)„ in the presence of ROH (R = Me; R = n-Pr) gives four major products, n-C6H13(Me)Si(OH)H, H(n-C6H13)(Me)Si-(n-C6H13)(Me)SiH, H(n-C6H13)(Me)Si-(n-C6H13)(Me)SiOR, and (RO)(n-C6HI3)(Me)Si-(n-C6H13)(Me)SiOR. To explain these results, a photolytic cascade mechanism that involves both the extrusion of silylene units and the formation of silyl radical terminated polymer fragments is proposed. The photochemistry of phenyl-substituted polysilane polymers was examined and found to be considerably more complex than the photochemistry of the alkyl-substituted polymers. © 1985, American Chemical Society. All rights reserved.
Peter Trefonas, James R. Damewood, et al.
Organometallics
Willie E. Rochefort, Glenn W. Heffner, et al.
Macromolecules
Kenneth R. Carter, Richard A. DiPietro, et al.
American Chemical Society, Polymer Preprints, Division of Polymer Chemistry
Robert D. Miller, Andreas Heise, et al.
American Chemical Society, Polymer Preprints, Division of Polymer Chemistry