Oxygenation of cobalt porphyrinates: coordination or oxidation?

Inorganic Chemistry
Jianfeng LiW Robert Scheidt

Abstract

The X-ray characterization of the five-coordinate picket-fence porphyrin complex, [Co(TpivPP)(2-MeHIm)], is reported. The complex has the displacement of cobalt from the porphyrin plane = 0.15 A, and Co-N(Im) = 2.145(3) and (Co-N(p))(av) = 1.979(3) A. This five-coordinate complex, in the presence of dioxygen and excess 2-methylimidazole, undergoes an unanticipated, photoinitiated atropisomerization of the porphyrin ligand, oxidation of cobalt(II), and the formation of the neutral cobalt(III) complex [Co(alpha,alpha,beta,beta-TpivPP)(2-MeHIm)(2-MeIm(-)]. Two distinct examples of this complex have been structurally characterized, and both have structural parameters consistent with cobalt(III). The two new Co(III) porphyrin complexes have axial Co-N(Im) distances ranging from 1.952 to 1.972 A, but which allow for the distinction between imidazole and imidazolate. An interesting intermolecular hydrogen bonding network is observed that leads to infinite helical chains. UV-vis spectroscopic study suggests that [Co(TpivPP)(2-MeHIm)(O(2))] is an intermediate state for the oxidation reaction and that the atropisomerization process is photocatalyzed. A reaction route is proposed based on the spectroscopic studies.

References

Feb 1, 1978·Proceedings of the National Academy of Sciences of the United States of America·J P CollmanK S Suslick
Mar 19, 1975·Journal of the American Chemical Society·J P CollmanW T Robinson
Oct 1, 1970·Proceedings of the National Academy of Sciences of the United States of America·B M Hoffman, D H Petering
Oct 1, 1972·Proceedings of the National Academy of Sciences of the United States of America·J C Chien, L C Dickinson
Oct 16, 1974·Journal of the American Chemical Society·J P CollmanH Ljusberg-Wahren
Jan 1, 1973·Annals of the New York Academy of Sciences·J L Hoard
Dec 1, 1973·Proceedings of the National Academy of Sciences of the United States of America·J L Hoard, W R Scheidt
Feb 21, 1973·Journal of the American Chemical Society·F A Walker
Mar 21, 1973·Journal of the American Chemical Society·D V StynesJ A Ibers
Nov 22, 1967·Journal of the American Chemical Society·J Simplicio, R G Wilkins
May 31, 2002·Acta Crystallographica. Section B, Structural Science·Frank H Allen
May 31, 2002·Acta Crystallographica. Section B, Structural Science·Ian J BrunoRobin Taylor
Dec 16, 2004·Journal of Inorganic Biochemistry·W Robert ScheidtJ Timothy Sage
Jan 27, 2005·Journal of the American Chemical Society·Yujiang SongJohn A Shelnutt
May 9, 2006·Inorganic Chemistry·Chuanjiang HuW Robert Scheidt
Feb 15, 2008·Journal of the American Chemical Society·Chuanjiang HuW Robert Scheidt

❮ Previous
Next ❯

Citations

May 31, 2012·Journal of the American Chemical Society·Jianfeng LiW Robert Scheidt
Nov 10, 2014·The Journal of Chemical Physics·Niloufar ShafizadehPhilippe Maillard
Apr 29, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Qiang YuJianfeng Li
Mar 27, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Kolanu SudhakarZeev Gross
May 28, 2019·Nature Communications·Jianping ZhaoJianfeng Li
Aug 6, 2019·Chemistry : a European Journal·Michał J BiałekLechosław Latos-Grażyński
Apr 26, 2014·Acta Crystallographica. Section E, Structure Reports Online·Yassine BelghithHabib Nasri
Jun 8, 2011·Angewandte Chemie·Katsunori YamanishiFumio Uchida
Jul 7, 2015·Acta Crystallographica. Section C, Structural Chemistry·Qiang YuJianfeng Li
Apr 24, 2021·European Journal of Organic Chemistry·Karolis NorvaišaMathias O Senge
May 6, 2021·Inorganic Chemistry·Jianping ZhaoZeyuan Lin
Sep 13, 2013·Journal of the American Chemical Society·Jianfeng LiW Robert Scheidt

❮ 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.