title: Heterogeneous rate constants for indium mediated allylations: cinnamyl chloride in ethanol/water mixtures.
abstract: Indium mediated allylation (IMA) offers a powerful tool to synthetic chemists for creating carbon-carbon bonds. However, its rate limiting step, the heterogeneous reaction of allyl halides at solid indium surfaces, is still poorly understood. For example, solvent effects, especially the presence of water, on IMA are dramatic. We report for the first time rate constants for the heterogeneous rate limiting step of IMA. The rate constant for reaction of cinnamyl chloride on indium decreases from 5.5 × 10(-4) cm/s in 80% ethanol/20% water to 1 × 10(-4) cm/s in 99.8% ethanol/0.2% water. In addition, the percent water has a dramatic effect on induction time. This study further establishes photomicroscopy as a powerful tool for the determination of heterogeneous rate constants.
authors.affiliation: Department of Chemistry, Hobart and William Smith Colleges , Geneva, New York 14456, United States.
authors.forename: Alexa N
authors.initials: AN
authors.lastname: Hill
authors.forename: Katherine M
authors.initials: KM
authors.lastname: Delaney
authors.forename: Tessa R
authors.initials: TR
authors.lastname: Sullivan
authors.forename: Gabriella
authors.initials: G
authors.lastname: Mylod
authors.forename: Katrina H
authors.initials: KH
authors.lastname: Kiesow
authors.forename: Walter J
authors.initials: WJ
authors.lastname: Bowyer