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Photocatalysis of Chloroform Decomposition by the Hexachlororuthenate( IV ) Ion
Author(s) -
Chan Alissa M.,
Peña Laura A.,
Segura Rosa E.,
Auroprem Ramya,
Harvey Brent M.,
Brooke Caroline M.,
Hoggard Patrick E.
Publication year - 2012
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/php.12005
Subject(s) - chemistry , chloroform , photochemistry , dissociation (chemistry) , chloride , decomposition , photocatalysis , photodissociation , irradiation , ion , inorganic chemistry , phosgene , coordination sphere , chemical decomposition , catalysis , organic chemistry , physics , nuclear physics
Dissolved hexachlororuthenate( IV ) effectively catalyzes the photodecomposition of chloroform to hydrogen chloride and phosgene under near‐ UV (λ > 345 nm) irradiation, whereby RuCl 6 2− is not itself photocatalytically active, but is photochemically transformed into a species that is active, possibly RuCl 5 (CHCl 3 ) − . Conversion to a photoactive species during irradiation is consistent with the acceleration of the decomposition rate during the early stages and with the apparent inverse dependence of the decomposition rate on the initial concentration of RuCl 6 2− . The displacement of Cl − by CHCl 3 in the coordination sphere to create the photoactive species is consistent with the retardation of photodecomposition by both Cl − and H 2 O. The much smaller photodecomposition rate in CDCl 3 suggests that C–H bond dissociation occurs during the primary photochemical event, which is also consistent with the presence of a CHCl 3 molecule in the first coordination sphere.