Abstract
Aminosilanes possess the appropriate structural features for use as two-electron sensitizers in silver halide photography. Here, we describe studies of the nucleophile-assisted cleavage reactions of the C - Si bonds in their radical cations. Water is identified as a useful nucleophile. It is found that the kinetics of these reactions are best described by taking into account a radical cation - water complex. The cleavage reactions are also controlled by steric effects at silicon and by the proximity of a carboxylate group that can modify the nucleophilicity of the water. Cleavage forms an α-amino radical that can donate a second electron to 9,10-dicyanoanthracene as a solution-phase electron acceptor.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 777-788 |
| Number of pages | 12 |
| Journal | Canadian Journal of Chemistry |
| Volume | 81 |
| Issue number | 6 |
| DOIs | |
| State | Published - Jun 1 2003 |
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Keywords
- Fragmentation
- Radical cation
- Silane
- Steric effects
- Two-electron sensitization
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Aminosilanes as two-electron donors : A technological application of radical cation chemistry. / Gould, Ian; Godleski, Stephen A.; Zielinski, Paul A.; Farid, Samir.
In: Canadian Journal of Chemistry, Vol. 81, No. 6, 01.06.2003, p. 777-788.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Aminosilanes as two-electron donors
T2 - A technological application of radical cation chemistry
AU - Gould, Ian
AU - Godleski, Stephen A.
AU - Zielinski, Paul A.
AU - Farid, Samir
PY - 2003/6/1
Y1 - 2003/6/1
N2 - Aminosilanes possess the appropriate structural features for use as two-electron sensitizers in silver halide photography. Here, we describe studies of the nucleophile-assisted cleavage reactions of the C - Si bonds in their radical cations. Water is identified as a useful nucleophile. It is found that the kinetics of these reactions are best described by taking into account a radical cation - water complex. The cleavage reactions are also controlled by steric effects at silicon and by the proximity of a carboxylate group that can modify the nucleophilicity of the water. Cleavage forms an α-amino radical that can donate a second electron to 9,10-dicyanoanthracene as a solution-phase electron acceptor.
AB - Aminosilanes possess the appropriate structural features for use as two-electron sensitizers in silver halide photography. Here, we describe studies of the nucleophile-assisted cleavage reactions of the C - Si bonds in their radical cations. Water is identified as a useful nucleophile. It is found that the kinetics of these reactions are best described by taking into account a radical cation - water complex. The cleavage reactions are also controlled by steric effects at silicon and by the proximity of a carboxylate group that can modify the nucleophilicity of the water. Cleavage forms an α-amino radical that can donate a second electron to 9,10-dicyanoanthracene as a solution-phase electron acceptor.
KW - Fragmentation
KW - Radical cation
KW - Silane
KW - Steric effects
KW - Two-electron sensitization
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UR - http://www.scopus.com/inward/citedby.url?scp=0041732395&partnerID=8YFLogxK
U2 - 10.1139/v03-073
DO - 10.1139/v03-073
M3 - Article
VL - 81
SP - 777
EP - 788
JO - Canadian Journal of Chemistry
JF - Canadian Journal of Chemistry
SN - 0008-4042
IS - 6
ER -