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Article: Water-Catalyzed Dehalogenation Reactions of Isobromoform and Its Reaction Products
Title | Water-Catalyzed Dehalogenation Reactions of Isobromoform and Its Reaction Products |
---|---|
Authors | |
Issue Date | 2004 |
Publisher | American 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? |
Abstract | A 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 Identifier | http://hdl.handle.net/10722/70304 |
ISSN | 2023 Impact Factor: 14.4 2023 SCImago Journal Rankings: 5.489 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
---|---|---|
dc.contributor.author | Kwok, WM | en_HK |
dc.contributor.author | Zhao, C | en_HK |
dc.contributor.author | Li, YL | en_HK |
dc.contributor.author | Guan, X | en_HK |
dc.contributor.author | Wang, D | en_HK |
dc.contributor.author | Phillips, DL | en_HK |
dc.date.accessioned | 2010-09-06T06:21:37Z | - |
dc.date.available | 2010-09-06T06:21:37Z | - |
dc.date.issued | 2004 | en_HK |
dc.identifier.citation | Journal Of The American Chemical Society, 2004, v. 126 n. 10, p. 3119-3131 | en_HK |
dc.identifier.issn | 0002-7863 | en_HK |
dc.identifier.uri | http://hdl.handle.net/10722/70304 | - |
dc.description.abstract | A 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.language | eng | en_HK |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html | en_HK |
dc.relation.ispartof | Journal of the American Chemical Society | en_HK |
dc.title | Water-Catalyzed Dehalogenation Reactions of Isobromoform and Its Reaction Products | en_HK |
dc.type | Article | en_HK |
dc.identifier.openurl | http://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.email | Phillips, DL:phillips@hku.hk | en_HK |
dc.identifier.authority | Phillips, DL=rp00770 | en_HK |
dc.description.nature | link_to_subscribed_fulltext | - |
dc.identifier.doi | 10.1021/ja0390552 | en_HK |
dc.identifier.scopus | eid_2-s2.0-1642307124 | en_HK |
dc.identifier.hkuros | 90609 | en_HK |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-1642307124&selection=ref&src=s&origin=recordpage | en_HK |
dc.identifier.volume | 126 | en_HK |
dc.identifier.issue | 10 | en_HK |
dc.identifier.spage | 3119 | en_HK |
dc.identifier.epage | 3131 | en_HK |
dc.identifier.isi | WOS:000220192000040 | - |
dc.publisher.place | United States | en_HK |
dc.identifier.scopusauthorid | Kwok, WM=7103129332 | en_HK |
dc.identifier.scopusauthorid | Zhao, C=7403563836 | en_HK |
dc.identifier.scopusauthorid | Li, YL=27168456500 | en_HK |
dc.identifier.scopusauthorid | Guan, X=8313149700 | en_HK |
dc.identifier.scopusauthorid | Wang, D=7407071795 | en_HK |
dc.identifier.scopusauthorid | Phillips, DL=7404519365 | en_HK |
dc.identifier.issnl | 0002-7863 | - |