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.
Original language | English |
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Title of host publication | High performance computing in science and engineering, Garching / Munich 2007 |
Editors | S. Wagner, M. Steinmetz, A. Bode, M. Brehm |
Place of Publication | Heidelberg |
Publisher | Springer |
Pages | 210-212 |
Number of pages | 3 |
ISBN (Print) | 3540691812 |
Publication status | Published - 2009 |