Phototransformation of Perchlorate to Chloride in the Presence of Polysilanes

Download
  1. Get@NRC: Phototransformation of Perchlorate to Chloride in the Presence of Polysilanes (Opens in a new window)
DOIResolve DOI: http://doi.org/10.1071/CH07245
AuthorSearch for: ; Search for: ; Search for: ; Search for: ; Search for: ; Search for:
TypeArticle
Journal titleAustralian Journal of Chemistry
Volume60
Issue11
Pages857861; # of pages: 5
AbstractPerchlorate is a uniquely stable chemical described as an emerging thyroid disrupting agent that is presently detected in several terrestrial and aquatic matrices. The present study was undertaken to deoxygenate perchlorate to the chloride anion photolytically in the presence of dodecamethylcyclohexasilane (Me2Si)6 1. It is found that photolysis of 1 in the presence of dry NaClO4 in tetrahydrofuran (THF) at 254 nm leads to the disappearance of the salt. The removal of ClO4– occurred with the concurrent formation of ClO3– and ClO2–, which disappear to eventually produce the chloride anion quantitatively. The two cyclic silanes (Me2Si)5 3 and (Me2Si)4 4 in addition to several other siloxanes that include (Me2SiO)3, (Me2SiO)4, and (Me2Si)xO2 (x = 4 and 5) were also detected. When the reaction was repeated using uniformly labelled 18O-[ClO4–] it was found that oxygen incorporated in the siloxane products was derived from perchlorate. Mixing 1 with perchlorate in THF in the dark or adding the salt to 1 after the latter being photolyzed in THF did not deoxygenate ClO4–. Based on experimental evidence gathered thus far it is concluded that dimethylsilylene, Me2Si: 2, a reactive intermediate produced by the photolysis of 1, is in part responsible for the deoxygenation of perchlorate. Direct oxygen transfer from ClO4– to the silanes during photolysis is also suggested as a potential route of deoxygenating ClO4–.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada; NRC Biotechnology Research Institute
Peer reviewedNo
NRC number49084
NPARC number3539409
Export citationExport as RIS
Report a correctionReport a correction
Record identifier32816ee2-9bdd-43fb-a7c5-b89097fd663b
Record created2009-03-01
Record modified2016-05-09
Bookmark and share
  • Share this page with Facebook (Opens in a new window)
  • Share this page with Twitter (Opens in a new window)
  • Share this page with Google+ (Opens in a new window)
  • Share this page with Delicious (Opens in a new window)