𝔖 Bobbio Scriptorium
✦   LIBER   ✦

On the O2 binding of Fe–porphyrin, Fe–porphycene, and Fe–corrphycene complexes

✍ Scribed by Hiroyuki Nakashima; Jun-ya Hasegawa; Hiroshi Nakatsuji

Publisher
John Wiley and Sons
Year
2006
Tongue
English
Weight
337 KB
Volume
27
Category
Article
ISSN
0192-8651

No coin nor oath required. For personal study only.

✦ Synopsis

Abstract

Based on our previous study for the O~2~ binding of the Fe–Por complex, this study investigates the O~2~ binding mechanism in the Fe–porphyrin isomers, Fe–porphycene (FePc), and Fe–corrphycene (FeCor) complexes. By calculating the potential energy surface of the O~2~ binding, the present study explains the reason for the dramatic increase of O~2~ affinities observed in the FePc complex. In the case of FeCor–O~2~, the O~2~ binding process includes the intersystem crossing from a triplet to singlet state, as in the FePor–O~2~ complex. However, FePc–O~2~ uses only a singlet surface. This is because the ground state of the FePc complex in the deoxy state is a triplet state, while those of FePor and FeCor are a quintet state. Such difference originates from character of the SOMO. We estimated an equilibrium constant for the O~2~ binding that reasonably reproduced the trend observed in the experiments. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 1363–1372, 2006

📜 SIMILAR VOLUMES

On the reversible O2 binding of the Fe–p
On the reversible O2 binding of the Fe–porphyrin complex
✍ Hiroyuki Nakashima; Jun-Ya Hasegawa; Hiroshi Nakatsuji 📂 Article 📅 2006 🏛 John Wiley and Sons 🌐 English ⚖ 250 KB

## Abstract Electronic mechanism of the reversible O~2~ binding by heme was studied by using Density Functional Theory calculations. The ground state of oxyheme was calculated to be open singlet state [Fe(S =1/2) + O~2~(S = 1/2)]. The potential energy surface for singlet state is associative, while

On the electronic structure and bonding
On the electronic structure and bonding of the intriguing mixed Fe2+/Fe3+ [{Cp(CO)2Fe}tBuPO2FeCl2]2-Complex
✍ Ingo-Peter Lorenz; Markus Maier; Axel Schulz 📂 Article 📅 2005 🏛 John Wiley and Sons 🌐 English ⚖ 324 KB

## Abstract The structure and bonding of [{Cp(CO)~2~Fe}^t^BuPO~2~FeCl~2~]~2~(**2**) have been investigated theoretically and experimentally. The molecular orbitals of **2** have been calculated to investigate the question why this type of complex forms a planar ring system. The electronic configura

The effects of chlorine on Fe and Fe2O3
The effects of chlorine on Fe and Fe2O3 surfaces in H2S environment
✍ Jagdish Prasad; Eric Murray; Jeffry A. Kelber 📂 Article 📅 1992 🏛 Elsevier Science 🌐 English ⚖ 190 KB

We have used X-ray photoelectron spectroscopy to study the effects of chlorine gas on Fe and Fe203 surfaces pre-exposed to H2S at 105 K. H2S chemisorbs on the Fe203 surface at 105 K to form adsorbed sulfur (S,) and sulfylhydril (SH,) intermediates. Subsequent exposure to C12 vapor at 105 K results i