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Redox Catalysis and Reactivity of Metalloporphyrines

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High Performance Computing in Science and Engineering, Garching/Munich 2007

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Abstract

Ab initio and density-functional theory (DFT) calculations on the Cu(II)-catalyzed rearrangement of quadricyclane to norbornadiene suggest that reaction proceeds via electron-transfer from the surface/CuSO4 to the hydrocarbon.

The mechanisms of direct porphyrin metalation was investigated using density functional theory (DFT) calculations for the gas-phase reactions of the unsubstituted porphyrin with the metals Fe, Co, Ni, Cu and Zn. The related reaction of tetraphenylporphyrin with bare metal atoms (Co and Zn) was studied with X-ray photoelectron spectroscopy, scanning tunneling microscopy, and temperature-programmed reaction measurements on ordered monolayer films of the molecules adsorbed on a Ag(111) surface. DFT calculations suggest that metalations with Fe, Co and Ni show two-state reactivity, while those with Cu and Zn proceed on a single potential energy surface. For metalation with Zn, we calculated a barrier of the first hydrogen transfer step of 32.6 kcal mol−1, in a good agreement with the overall experimental activation energy of 31 kcal mol−1.

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Authors and Affiliations

  1. Computer-Chemie-Centrum der Friedrich-Alexander Universität Erlangen-Nürnberg, Nägelsbachstraße 25, 91052, Erlangen, Germany

    Tatyana E. Shubina & Timothy Clark

Authors
  1. Tatyana E. Shubina
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  2. Timothy Clark
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Correspondence to Tatyana E. Shubina .

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Editors and Affiliations

  1. Institut für Aerodynamik und Gasdynamik, Universität Stuttgart, Pfaffenwaldring 21, 70550, Stuttgart, Germany

    Siegfried Wagner

  2. Astrophysikalisches Institut Potsdam, An der Sternwarte 16, 14482, Potsdam, Germany

    Matthias Steinmetz

  3. Lehrstuhl für Rechnertechnik und Rechnerorganisation, Technische Universität München, Boltzmannstr. 3, 85748, Garching b. München, Germany

    Arndt Bode

  4. Leibniz-Rechenzentrum, Boltzmannstr. 1, 85748, Garching b. München, Germany

    Matthias Brehm

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Shubina, T.E., Clark, T. (2009). Redox Catalysis and Reactivity of Metalloporphyrines. In: Wagner, S., Steinmetz, M., Bode, A., Brehm, M. (eds) High Performance Computing in Science and Engineering, Garching/Munich 2007. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-540-69182-2_16

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