PMID: 11916394Mar 28, 2002Paper

"True" iron(V) and iron(VI) porphyrins: a first theoretical exploration

Journal of the American Chemical Society
Abhishek Dey, Abhik Ghosh

Abstract

We present here a first theoretical characterization of iron(V) (S = (3)/(2)) and iron(VI) (S = 0) porphyrin intermediates. The Fe(V) calculations exhibit exceptionally narrow convergence radii and we believe that for this reason they have long eluded researchers working on high-valent iron intermediates. The Fe(V)-N(nitrido) bond distance in the DFT(PW91/TZP) optimized geometry of Fe(V)(P)(N) is 1.722 A, comparable to and slightly longer than the Fe(IV)-O bond distance of 1.684 A in Fe(IV)(P)(O) and the Fe(IV)-N(imido) bond distance of 1.698 A in Fe(IV)(P)(NH). In contrast, the Fe(VI)-N(nitrido) bond distances in [Fe(VI)(P)(N)](+) (S = 0) and Fe(VI)(P)(N)(F) (S = 0) are dramatically shorter, 1.508 and 1.533 A, respectively, consistent with the formal triple bond character of the Fe(VI)-N(nitrido) bond. The nitrido ligand appears to be uniquely capable of stabilizing a "true" Fe(V) center, in the sense defined in the paper. All three unpaired electrons in Fe(V)(P)(N) are completely localized on the Fe(V)-N(nitrido) axis, with the Fe and N gross atomic spin populations being 1.579 and 1.550, respectively. In contrast, an axial ligand set consisting of an oxide and a fluoride do not stabilize an Fe(V) ground state but favor an el...Continue Reading

References

Sep 13, 2001·Journal of the American Chemical Society·M T Green
Nov 20, 2001·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·R WeissA X Trautwein
Nov 20, 2001·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Y Watanabe

❮ Previous
Next ❯

Citations

Sep 15, 2004·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Wonwoo NamWoon Ju Song
Jul 15, 2006·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Abhik Ghosh
May 9, 2008·Chemical Communications : Chem Comm·Akira IkezakiMikio Nakamura
May 9, 2014·Physical Chemistry Chemical Physics : PCCP·Azaj Ansari, Gopalan Rajaraman
Feb 19, 2005·Angewandte Chemie·Andrea Decker, Edward I Solomon
Nov 25, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Jeremy M Smith, Deepak Subedi
May 23, 2015·Chemical Communications : Chem Comm·Tse-Hong ChenRui Zhang
Jan 13, 2006·Proceedings of the National Academy of Sciences of the United States of America·Kazunobu KonishiMichihiko Kobayashi
Jul 28, 2005·Journal of Molecular Modeling·Haiyan WangKean Li
Mar 20, 2018·Journal of Inorganic Biochemistry·Ngo Fung LeeRui Zhang
Feb 6, 2009·Journal of the American Chemical Society·Zhengzheng PanMartin Newcomb
Sep 20, 2005·Biochemical and Biophysical Research Communications·Martin Newcomb, R Esala P Chandrasena
Apr 12, 2011·Journal of Chemical Theory and Computation·Mariusz RadońKristine Pierloot
Oct 11, 2011·Journal of Chemical Theory and Computation·Hui ChenSason Shaik
Feb 19, 2008·Journal of the American Chemical Society·Barbara ChiavarinoAndrea Lapi
Oct 6, 2005·Journal of the American Chemical Society·Dilusha N HarischandraMartin Newcomb
Apr 6, 2006·Journal of the American Chemical Society·Martin NewcombStephen G Sligar

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.