Shubina T, Clark T (2009)
Publication Status: Published
Publication Type: Authored book
Publication year: 2009
Pages Range: 201-212
DOI: 10.1007/978-3-540-69182-2_16
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).
APA:
Shubina, T., & Clark, T. (2009). Redox Catalysis and Reactivity of Metalloporphyrines.
MLA:
Shubina, Tatyana, and Timothy Clark. Redox Catalysis and Reactivity of Metalloporphyrines. 2009.
BibTeX: Download