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Redox Catalysis and Reactivity of Metalloporphyrines

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

Author

Listed:
  • Tatyana E. Shubina

    (Computer-Chemie-Centrum der Friedrich-Alexander Universität Erlangen-Nürnberg)

  • Timothy Clark

    (Computer-Chemie-Centrum der Friedrich-Alexander Universität Erlangen-Nürnberg)

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.

Suggested Citation

  • Tatyana E. Shubina & Timothy Clark, 2009. "Redox Catalysis and Reactivity of Metalloporphyrines," Springer Books, in: Siegfried Wagner & Matthias Steinmetz & Arndt Bode & Matthias Brehm (ed.), High Performance Computing in Science and Engineering, Garching/Munich 2007, pages 201-212, Springer.
    • Handle: RePEc:spr:sprchp:978-3-540-69182-2_16
    DOI: 10.1007/978-3-540-69182-2_16
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