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The reaction mechanism and the regioselectivity of this enzyme are investigated by using density functional calculations. Four different substrates, namely, perchloroethylene, trichloroethylene, <jats:italic>cis<\/jats:italic>\u2010dichloroethylene, and chlorotheylene, have been considered and were found to follow the same reaction mechanism pattern. The reaction starts with the reduction of Co<jats:sup>II<\/jats:sup> to Co<jats:sup>I<\/jats:sup> through a proton\u2010coupled electron transfer process, with the proton delivered to a Tyr246 anion. This is followed by concerted C\u2212Cl bond heterolytic cleavage and proton transfer from Tyr246 to the substrate carbon atom, generating a Co<jats:sup>III<\/jats:sup>\u2212Cl intermediate. Subsequently, a one\u2010electron transfer leads to the formation of the Co<jats:sup>II<\/jats:sup>\u2212Cl product, from which the chloride and the dehalogenated product can be released from the active site. The substrate reactivity follows the trend perchloroethylene&gt;trichloroethylene\u226b<jats:italic>cis<\/jats:italic>\u2010dichloroethylene\u226bchlorotheylene. The barriers for the latter two substrates are significantly higher compared with those for perchloroethylene and trichloroethylene, implying that PceA does not catalyze their degradation. In addition, the formation of <jats:italic>cis<\/jats:italic>\u2010dichloroethylene has a lower barrier by 3.8\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup> than the formation of <jats:italic>trans<\/jats:italic>\u2010dichloroethylene and 1,1\u2010dichloroethylene, reproducing the regioselectivity. These results agree quite well with the experimental findings, which show <jats:italic>cis<\/jats:italic>\u2010dichloroethylene as the sole product in the PceA\u2010catalyzed dechlorination of perchloethylene and trichloroethylene.<\/jats:p>","DOI":"10.1002\/chem.201601575","type":"journal-article","created":{"date-parts":[[2016,7,26]],"date-time":"2016-07-26T09:38:30Z","timestamp":1469525910000},"page":"12391-12399","source":"Crossref","is-referenced-by-count":33,"title":["Unraveling the Mechanism and Regioselectivity of the B12\u2010Dependent Reductive Dehalogenase PceA"],"prefix":"10.1002","volume":"22","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8989-6928","authenticated-orcid":false,"given":"Rong\u2010Zhen","family":"Liao","sequence":"first","affiliation":[{"name":"Key Laboratory of Material Chemistry for Energy Conversion and Storage Ministry of Education Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica Hubei Key Laboratory of Materials Chemistry and Service Failure School of Chemistry and Chemical Engineering Huazhong University of Science and Technology  Wuhan 430074 P. 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