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Please use this identifier to cite or link to this item: http://hdl.handle.net/123456789/12677

Title: Density functional theory study of the mechanisms of oxidation of ethylene by chromyl chloride
Authors: Tia, Richard
Adei, Evans
Issue Date: 11-May-2009
Publisher: American Chemical Society
Citation: Inorg. Chem.2009,48, 11434–11443DOI: 10.1021/ic901648y
Abstract: The mechanistic pathways for the formation of epoxide, 1,2-dichloroethane, 1,2-chlorohydrin, acetaldehyde, and vinylalcohol precursors in the oxidation of ethylene by chromyl chloride has been studied using hybrid density functionaltheory at the B3LYP/LACVP* level of theory. The formation of the epoxide precursor(Cl2(O)Cr-OC2H4)was found totake place via initial[2þ2]addition of ethylene across the CrdO bonds of CrO2Cl2to form a chromaoxetaneintermediate. The pathway involving initial[3þ2]addition of ethylene to the oxygen and chlorine atoms of CrO2Cl2,which has not been explored in earlier studies, was found to be favored over[3þ2]addition of olefin to two oxygenatoms of CrO2Cl2. The formation of the 1,2-dichloroethane precursor, which was found to take place via[3þ2]addition of ethylene to two chlorine atoms of CrO2Cl2, is slightly favored over the formation of the epoxide precursor.The 1,2-chlorohydrin precursor has been found to originate from[3þ2]addition of ethylene to the oxygen and chlorineatoms of CrO2Cl2as opposed to[2þ2]addition of ethylene to the Cr-Cl bond. The vinyl alcohol precursorOdCrCl2-(OH)CHdCH2has been found to exist only on the triplet potential energy surface. The acetaldehydeprecursor(OdCrCl2-OCHCH3)was found to be the most stable species on the reaction surface. Hydrolysis may berequired to generate the epoxide, 1,2-dichloroethane and 1,2-chlorohydrin from the respective precursors.
Description: An article published by American Chemical Society and also available DOI: 10.1021/ic901648y
URI: http://hdl.handle.net/123456789/12677
Appears in Collections:College of Science

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