Triplet States of Tetrazoles, Nitrenes, and Carbenes from Matrix Photolysis of Tetrazoles, and Phenylcyanamide as a Source of Phenylnitrene

The Journal of Physical Chemistry. a
Manabu AbeCurt Wentrup

Abstract

Photolysis of 1- and 5-aryltetrazoles at 5-10 K using a 266 nm laser immediately generates their triplet excited states, which are characterized by their electron spin resonance (ESR) spectra with zero-field splitting parameters D = 0.12-0.13 cm-1 and E = 0.002-0.008 cm-1. Further photolysis of all of the aryltetrazoles affords arylnitrenes ( D ≅ 1 cm-1), and in the case of 5-aryltetrazoles also arylcarbenes ( D ≅ 0.5 cm-1). The formation of arylnitrenes from 5-aryltetrazoles, where no aryl-N bond is present, is explained by the photochemical rearrangement of initially formed nitrile imines ArCN+N-R to carbodiimides. The monosubstituted carbodiimide PhN═C═NH isomerizes to phenylcyanamide, PhNH-CN, and photolysis of the latter causes rapid elimination of HCN and formation of phenylnitrene. When N-methyl groups are present in the tetrazoles, methylnitrene, CH3-N, is formed too. In the case of 5-phenyltetrazole, additional hydrogen shift and fragmentation afford cyano- and isocyanonitrenes, NCN and CNN.

References

Jun 24, 2004·Journal of the American Chemical Society·Tadatake SatoWolfram Sander
Mar 1, 2012·Journal of the American Chemical Society·Didier BéguéCurt Wentrup
Jul 26, 2013·Chemical Reviews·Manabu Abe
Oct 18, 2014·Journal of the American Chemical Society·David KvaskoffCurt Wentrup
Aug 6, 2015·Chemical Communications : Chem Comm·Cláudio M NunesCurt Wentrup
Feb 25, 2017·Chemical Reviews·Curt Wentrup
May 29, 2018·Angewandte Chemie·Curt Wentrup

❮ Previous
Next ❯

Citations

Nov 19, 2019·Macromolecular Rapid Communications·Yee Yee KhineMartina H Stenzel
Oct 10, 2018·The Journal of Physical Chemistry. a·Didier BéguéCurt Wentrup
Feb 23, 2019·The Journal of Physical Chemistry. a·Didier BéguéCurt Wentrup
Jan 29, 2019·The Journal of Physical Chemistry. a·Didier BéguéCurt Wentrup

❮ 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.

Related Papers

Tanpakushitsu kakusan koso. Protein, nucleic acid, enzyme
Hori Hiroshi
Physical Review. B, Condensed Matter
B DasR Reifenberger
Biochemical and Biophysical Research Communications
S J van der BentJ C Goedheer
© 2022 Meta ULC. All rights reserved