Aminosilanes as two-electron donors

A technological application of radical cation chemistry

Ian Gould, Stephen A. Godleski, Paul A. Zielinski, Samir Farid

Research output: Contribution to journalArticle

15 Citations (Scopus)

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 languageEnglish (US)
Pages (from-to)777-788
Number of pages12
JournalCanadian Journal of Chemistry
Volume81
Issue number6
DOIs
StatePublished - Jun 1 2003

Fingerprint

Cations
Nucleophiles
Positive ions
Electrons
Water
Silver halides
Photography
Silicon
Kinetics
9,10-dicyanoanthracene

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 journalArticle

Gould, Ian ; Godleski, Stephen A. ; Zielinski, Paul A. ; Farid, Samir. / Aminosilanes as two-electron donors : A technological application of radical cation chemistry. In: Canadian Journal of Chemistry. 2003 ; Vol. 81, No. 6. pp. 777-788.
@article{0e520c3147064c7d943c6bd52bd4f881,
title = "Aminosilanes as two-electron donors: A technological application of radical cation chemistry",
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.",
keywords = "Fragmentation, Radical cation, Silane, Steric effects, Two-electron sensitization",
author = "Ian Gould and Godleski, {Stephen A.} and Zielinski, {Paul A.} and Samir Farid",
year = "2003",
month = "6",
day = "1",
doi = "10.1139/v03-073",
language = "English (US)",
volume = "81",
pages = "777--788",
journal = "Canadian Journal of Chemistry",
issn = "0008-4042",
publisher = "National Research Council of Canada",
number = "6",

}

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

UR - http://www.scopus.com/inward/record.url?scp=0041732395&partnerID=8YFLogxK

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 -