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Catalytically Active Cu(II)-Pybox Complexes: Insights by EPR Spectroscopy and DFT Computations

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Abstract

This paper addresses the geometry of the catalytic Cu(II) complexes formed in the course of stereoselective Diels–Alder reaction. The parent catalyst is [Cu(II)-isopropyl-pybox](OTf)2. Ethyl glyoxylate serves as dienophile and it reacts with 1,3-cyclohexadiene. The reaction is followed by CW EPR, HYSCORE, and (pulsed) ENDOR spectroscopy and the experimental results are supported by DFT computations. It is shown that during the catalytic process, the Cu(II) complex is pentacoordinated and one of the triflate counterions is coordinated to the Cu(II) center in axial position.

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Acknowledgments

This work was supported by Austrian Science Fund (FWF), Projects Nos. P19711 and P23847.

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Author notes

  1. V. Umamaheswari

    Present address: Erlangen Catalysis Resource Center, University of Erlangen-Nürnberg, Egerlandstrasse 3, 91058, Erlangen, Germany

Authors and Affiliations

  1. Institute of Physical and Theoretical Chemistry, Graz University of Technology, NAWI Graz, Stremayrgasse 9, 8010, Graz, Austria

    V. Umamaheswari, Pawel Cias & Georg Gescheidt

  2. Faculty of Physics and Earthscience, University of Leipzig, Linnéstr. 5, 04103, Leipzig, Germany

    Andreas Pöppl

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  1. V. Umamaheswari
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  2. Pawel Cias
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Correspondence to Pawel Cias.

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Umamaheswari, V., Cias, P., Pöppl, A. et al. Catalytically Active Cu(II)-Pybox Complexes: Insights by EPR Spectroscopy and DFT Computations. Appl Magn Reson 45, 667–679 (2014). https://doi.org/10.1007/s00723-014-0545-3

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  • DOI: https://doi.org/10.1007/s00723-014-0545-3

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