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

The present paper gives insight into an intramolecular dechlorination reaction involving Copper (I) and an ArCH2Cl moiety. The discussion of the presence of a Cu-III 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-Cu-I 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

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)

© Theoretical Chemistry Accounts: Theory, Computation, and Modeling, 2013, vol. 132, núm. 5, p. 1353

Springer Verlag

Author: Poater Teixidor, Albert
Cavallo, Luigi
Date: 2013
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 Cu-III 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-Cu-I 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
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)
Format: application/pdf
ISSN: 1432-881X (versió paper)
1432-2234 (versió electrònica)
Document access: http://hdl.handle.net/10256/8651
Language: eng
Publisher: Springer Verlag
Collection: MICINN/PN 2012-2015/RYC-2009-05226
AGAUR/2011BE100793
Reproducció digital del document publicat a: http://dx.doi.org/10.1007/s00214-013-1353-9
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/293900
Is part of: © Theoretical Chemistry Accounts: Theory, Computation, and Modeling, 2013, vol. 132, núm. 5, p. 1353
Rights: Tots els drets reservats
Subject: Compostos organometàl·lics
Organometallic compounds
Reaccions de substitució
Substitution reactions
Title: Organometallic copper I, II or III species in an intramolecular dechlorination reaction
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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