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Article: Water-Catalyzed Dehalogenation Reactions of Isobromoform and Its Reaction Products

TitleWater-Catalyzed Dehalogenation Reactions of Isobromoform and Its Reaction Products
Authors
Issue Date2004
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html
Citation
Journal Of The American Chemical Society, 2004, v. 126 n. 10, p. 3119-3131 How to Cite?
AbstractA combined experimental and theoretical study of the photochemistry of CHBr 3 in pure water and in acetonitrile/water mixed solvents is reported that elucidates the reactions and mechanisms responsible for the photochemical conversion of the halogen atoms in CHBr 3 into three bromide ions in water solution. Ultraviolet excitation at 240 nm of CHBr 3 (9 × 10 -5 M) in water resulted in almost complete conversion into 3HBr leaving groups and CO (major product) and HCOOH (minor product) molecules. Picosecond time-resolved resonance Raman (ps-TR 3) experiments and ab initio calculations indicate that the water-catalyzed O-H insertion/HBr elimination reaction of isobromoform and subsequent reactions of its products are responsible for the production of the final products observed following ultraviolet excitation of CHBr 3 in water. These results have important implications for the phase-dependent behavior of polyhalomethane photochemistry and chemistry in water-solvated environments as compared to gas-phase reactions. The dissociation reaction of HBr into H + and Br - ions is the driving force for several O-H insertion and HBr elimination reactions and allows O-H and C-H bonds to be cleaved more easily than in the absence of water molecules. This water-catalysis by solvation of a leaving group and its dissociation into ions (e.g., H + and Br - in the examples investigated here) may occur for a wide range of chemical reactions taking place in water-solvated environments.
Persistent Identifierhttp://hdl.handle.net/10722/70304
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorKwok, WMen_HK
dc.contributor.authorZhao, Cen_HK
dc.contributor.authorLi, YLen_HK
dc.contributor.authorGuan, Xen_HK
dc.contributor.authorWang, Den_HK
dc.contributor.authorPhillips, DLen_HK
dc.date.accessioned2010-09-06T06:21:37Z-
dc.date.available2010-09-06T06:21:37Z-
dc.date.issued2004en_HK
dc.identifier.citationJournal Of The American Chemical Society, 2004, v. 126 n. 10, p. 3119-3131en_HK
dc.identifier.issn0002-7863en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70304-
dc.description.abstractA combined experimental and theoretical study of the photochemistry of CHBr 3 in pure water and in acetonitrile/water mixed solvents is reported that elucidates the reactions and mechanisms responsible for the photochemical conversion of the halogen atoms in CHBr 3 into three bromide ions in water solution. Ultraviolet excitation at 240 nm of CHBr 3 (9 × 10 -5 M) in water resulted in almost complete conversion into 3HBr leaving groups and CO (major product) and HCOOH (minor product) molecules. Picosecond time-resolved resonance Raman (ps-TR 3) experiments and ab initio calculations indicate that the water-catalyzed O-H insertion/HBr elimination reaction of isobromoform and subsequent reactions of its products are responsible for the production of the final products observed following ultraviolet excitation of CHBr 3 in water. These results have important implications for the phase-dependent behavior of polyhalomethane photochemistry and chemistry in water-solvated environments as compared to gas-phase reactions. The dissociation reaction of HBr into H + and Br - ions is the driving force for several O-H insertion and HBr elimination reactions and allows O-H and C-H bonds to be cleaved more easily than in the absence of water molecules. This water-catalysis by solvation of a leaving group and its dissociation into ions (e.g., H + and Br - in the examples investigated here) may occur for a wide range of chemical reactions taking place in water-solvated environments.en_HK
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.htmlen_HK
dc.relation.ispartofJournal of the American Chemical Societyen_HK
dc.titleWater-Catalyzed Dehalogenation Reactions of Isobromoform and Its Reaction Productsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0002-7863&volume=126&spage=3119&epage=3131&date=2004&atitle=Water-catalyzed+dehalogenation+reactions+of+isobromoform+and+its+reaction+products+en_HK
dc.identifier.emailPhillips, DL:phillips@hku.hken_HK
dc.identifier.authorityPhillips, DL=rp00770en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ja0390552en_HK
dc.identifier.scopuseid_2-s2.0-1642307124en_HK
dc.identifier.hkuros90609en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-1642307124&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume126en_HK
dc.identifier.issue10en_HK
dc.identifier.spage3119en_HK
dc.identifier.epage3131en_HK
dc.identifier.isiWOS:000220192000040-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridKwok, WM=7103129332en_HK
dc.identifier.scopusauthoridZhao, C=7403563836en_HK
dc.identifier.scopusauthoridLi, YL=27168456500en_HK
dc.identifier.scopusauthoridGuan, X=8313149700en_HK
dc.identifier.scopusauthoridWang, D=7407071795en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK

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