Organometallic copper I, II or III species in an intramolecular dechlorination reaction

Handle URI:
http://hdl.handle.net/10754/562683
Title:
Organometallic copper I, II or III species in an intramolecular dechlorination reaction
Authors:
Poater, Albert; Cavallo, Luigi ( 0000-0002-1398-338X )
Abstract:
The present paper gives insight into an intramolecular dechlorination reaction involving Copper (I) and an ArCH2Cl moiety. The discussion of the presence of a CuIII organometallic intermediate becomes a challenge, and because of the lack of clear experimental detection of this proposed intermediate, and due to the computational evidence that it is less stable than other isomeric species, it can be ruled out for the complex studied here. Our calculations are completely consistent with the key hypothesis of Karlin et al. that TMPA-CuI is the substrate of intramolecular dechlorination reactions as well as the source to generate organometallic species. However the organometallic character of some intermediates has been refused because computationally these species are less stable than other isomers. Thus this study constitutes an additional piece towards the full understanding of a class of reaction of biological relevance. Further, the lack of high energy barriers and deep energy wells along the reaction pathway explains the experimental difficulties to trap other intermediates. © Springer-Verlag Berlin Heidelberg 2013.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
Springer Verlag
Journal:
Theoretical Chemistry Accounts
Issue Date:
15-Mar-2013
DOI:
10.1007/s00214-013-1353-9
Type:
Article
ISSN:
1432881X
Sponsors:
AP is grateful to the European Commission (CIG09-GA-2011-293900), Spanish MICINN (Ramon y Cajal contract RYC-2009-05226), and Generalitat de Catalunya (2011BE100793). We also want to thank the referees' comments to improve the manuscript.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorPoater, Alberten
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2015-08-03T11:01:19Zen
dc.date.available2015-08-03T11:01:19Zen
dc.date.issued2013-03-15en
dc.identifier.issn1432881Xen
dc.identifier.doi10.1007/s00214-013-1353-9en
dc.identifier.urihttp://hdl.handle.net/10754/562683en
dc.description.abstractThe present paper gives insight into an intramolecular dechlorination reaction involving Copper (I) and an ArCH2Cl moiety. The discussion of the presence of a CuIII organometallic intermediate becomes a challenge, and because of the lack of clear experimental detection of this proposed intermediate, and due to the computational evidence that it is less stable than other isomeric species, it can be ruled out for the complex studied here. Our calculations are completely consistent with the key hypothesis of Karlin et al. that TMPA-CuI is the substrate of intramolecular dechlorination reactions as well as the source to generate organometallic species. However the organometallic character of some intermediates has been refused because computationally these species are less stable than other isomers. Thus this study constitutes an additional piece towards the full understanding of a class of reaction of biological relevance. Further, the lack of high energy barriers and deep energy wells along the reaction pathway explains the experimental difficulties to trap other intermediates. © Springer-Verlag Berlin Heidelberg 2013.en
dc.description.sponsorshipAP is grateful to the European Commission (CIG09-GA-2011-293900), Spanish MICINN (Ramon y Cajal contract RYC-2009-05226), and Generalitat de Catalunya (2011BE100793). We also want to thank the referees' comments to improve the manuscript.en
dc.publisherSpringer Verlagen
dc.subjectCuIIIen
dc.subjectDechlorinationen
dc.subjectDehalogenationen
dc.subjectDFT calculationsen
dc.subjectOrganometallicen
dc.subjectOrganometallic complexesen
dc.subjectTMPAen
dc.titleOrganometallic copper I, II or III species in an intramolecular dechlorination reactionen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalTheoretical Chemistry Accountsen
dc.contributor.institutionDepartament de Química and Institut de Química Computacional, Universitat de Girona, Campus de Montilivi, 17071 Gerona, Catalonia, Spainen
kaust.authorCavallo, Luigien
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