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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)

Springer Verlag

Director: Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca
Autor: Poater Teixidor, Albert
Cavallo, Luigi
Data: 2013
Resum: 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
Accés al document: http://hdl.handle.net/10256/8651
Llenguatge: eng
Editor: Springer Verlag
Col·lecció: info:eu-repo/semantics/altIdentifier/doi/10.1007/s00214-013-1353-9
info:eu-repo/semantics/altIdentifier/issn/1432-881X
info:eu-repo/semantics/altIdentifier/eissn/1432-2234
info:eu-repo/grantAgreement/MICINN//RYC-2009-05226/ES/RYC-2009-05226/
AGAUR/2011BE100793
info:eu-repo/grantAgreement/EC/FP7/293900/EU/Ab initio Statics and Molecular Dynamics Simulation of Olefin Metathesis Catalysts for pharmacological purposes/COMPUTEDRUG
Drets: Tots els drets reservats
Matèria: Compostos organometàl·lics
Organometallic compounds
Reaccions de substitució
Substitution reactions
Títol: Organometallic copper I, II or III species in an intramolecular dechlorination reaction
Tipus: info:eu-repo/semantics/article
Repositori: DUGiDocs

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