Phototransformation of Perchlorate to Chloride in the Presence of Polysilanes

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DOITrouver le DOI : http://doi.org/10.1071/CH07245
AuteurRechercher : ; Rechercher : ; Rechercher : ; Rechercher : ; Rechercher : ; Rechercher :
TypeArticle
Titre de la revueAustralian Journal of Chemistry
Volume60
Numéro11
Pages857861; nbre. de pages : 5
RésuméPerchlorate 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–.
Date de publication
Langueanglais
AffiliationConseil national de recherches Canada; Institut de recherche en biotechnologie du CNRC
Publications évaluées par des pairsNon
Numéro du CNRC49084
Numéro NPARC3539409
Exporter la noticeExport en format RIS
Signaler une correctionSignaler une correction
Identificateur de l’enregistrement32816ee2-9bdd-43fb-a7c5-b89097fd663b
Enregistrement créé2009-03-01
Enregistrement modifié2016-05-09
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