Title: Direct Measurements of Deuterium Kinetic Isotope Effects in Anionic, Gas-Phase Substitution and Elimination Reactions
Abstract:Reactions with dianion nucleophiles were used to determine deuterium kinetic isotope effects (KIE's) in gas-phase E2 and SN2 reactions. This approach allows for the direct identification of eliminatio...Reactions with dianion nucleophiles were used to determine deuterium kinetic isotope effects (KIE's) in gas-phase E2 and SN2 reactions. This approach allows for the direct identification of elimination and substitution products in the reactions of simple alkyl halides. In general, the E2 reactions give large KIE's (∼7) for perdeutero substrates; however, elimination isotope effects are attenuated in reactions that occur near the collision-controlled limit. In a very slow elimination, a large KIE (>20) is observed, presumably due to lifetime effects in the collision complex. The SN2 reactions all give secondary deuterium isotope effects near unity, with the exception of one system, where suppression of the E2 channel in the perdeutero substrate leads to an enhancement of the SN2 rate and causes a modest inverse isotope effect.Read More
Publication Year: 2007
Publication Date: 2007-04-11
Language: en
Type: article
Indexed In: ['crossref', 'pubmed']
Access and Citation
Cited By Count: 47
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