NDLI: Transition metal ion-assisted photochemical generation of alkyl halides and hydrocarbons from carboxylic acids

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Pestovsky, Oleg Bakac, Andreja Carraher, Jack M.
Description	Author Affiliation: Carraher JM ( Ames Laboratory and Chemistry Department, Iowa State University, Ames, IA 50011, USA.)
Abstract	Near-UV photolysis of aqueous solutions of propionic acid and aqueous $Fe^{3+}$ in the absence of oxygen generates a mixture of hydrocarbons ( ethane , ethylene and butane ), carbon dioxide, and $Fe^{2+}.$ The reaction becomes mildly catalytic (about five turnovers) in the presence of oxygen which converts a portion of alkyl radicals to oxidizing intermediates that reoxidize $Fe^{2+}.$ The photochemistry in the presence of halide ions $(X^{−}$ = $Cl^{−},$ $Br^{−})$ generates ethyl halides via halogen atom abstraction from $FeX_{n}^{3−n}$ by ethyl radicals. Near-quantitative yields of $C_{2}H_{5}X$ are obtained at ≥0.05 M $X^{−}.$ Competition experiments with $Co(NH_{3})_{5}Br^{2+}$ provided kinetic data for the reaction of ethyl radicals with $FeCl^{2+}$ (k = (4.0 ± 0.5) × $10^{6}$ $M^{−1}$ $s^{−1})$ and with $FeBr^{2+}$ (k = (3.0 ± 0.5) × $10^{7}$ $M^{−1}$ $s^{−1}).$ Photochemical decarboxylation of propionic acid in the presence of $Cu^{2+}$ generates ethylene and $Cu^{+}.$ Longer-chain acids also yield alpha olefins as exclusive products. These reactions become catalytic under constant purge with oxygen which plays a dual role. It reoxidizes $Cu^{+}$ to $Cu^{2+},$ and removes gaseous olefins to prevent accumulation of $Cu^{+}($ olefin ) complexes and depletion of $Cu^{2+}.$ The results underscore the profound effect that the choice of metal ions, the medium, and reaction conditions exert on the photochemistry of carboxylic acids .
ISSN	14779226
Issue Number	19
Journal	Dalton Trans.
Volume Number	41
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2012-05-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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