Document Detail

Mechanism of base-promoted dehydrochlorination of pentachloroethane: concerted or stepwise?
MedLine Citation:
PMID:  19309129     Owner:  NLM     Status:  PubMed-not-MEDLINE    
This paper reports a first-principles molecular dynamics simulation study of the microscopic mechanism of the base-catalyzed dehydrochlorination of pentachloroethane. So far the nature of the mechanism of this reaction is not understood: the concerted and stepwise mechanisms are under debate. By combining ab initio molecular dynamics with the method of constraints, we determine the reaction mechanism and associated free energy profile. We find that the reaction barrier is in good agreement with experimental findings and reveal that the reaction proceeds via a concerted mechanism. Our simulations provide no evidence for the presence of carbanion intermediate indicative of the stepwise pathway. This microscopic understanding will provide new implications for understanding the reduction of polyhalogenated alkanes and rational design of effective materials to treat these contaminants.
Xiandong Liu; Evert Jan Meijer
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  The journal of physical chemistry. A     Volume:  113     ISSN:  1520-5215     ISO Abbreviation:  J Phys Chem A     Publication Date:  2009 Apr 
Date Detail:
Created Date:  2009-04-09     Completed Date:  2009-07-14     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9890903     Medline TA:  J Phys Chem A     Country:  United States    
Other Details:
Languages:  eng     Pagination:  3542-4     Citation Subset:  -    
State Key Laboratory for Mineral Deposit Research, School of Earth Sciences and Engineering, Nanjing University, Nanjing 210093, People's Republic of China.
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