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.
Graphical Abstract
In this study we give insight into an intramolecular dechlorination reaction involving Copper (I) and an ArCH2Cl moiety. The discussion about a CuIII organometallic intermediate becomes a challenge, but DFT calculations, together with the lack of a clear experimental detection of this proposed intermediate, reveal its presence can be ruled out.
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Acknowledgments
AP is grateful to the European Commission (CIG09-GA-2011-293900), Spanish MICINN (Ramón y Cajal contract RYC-2009-05226), and Generalitat de Catalunya (2011BE100793). We also want to thank the referees’ comments to improve the manuscript.
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Published as part of the special collection of articles derived from the 8th Congress on Electronic Structure: Principles and Applications (ESPA 2012).
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Poater, A., Cavallo, L. Organometallic copper I, II or III species in an intramolecular dechlorination reaction. Theor Chem Acc 132, 1353 (2013). https://doi.org/10.1007/s00214-013-1353-9
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DOI: https://doi.org/10.1007/s00214-013-1353-9