Bioinspired oxidation of oximes to nitric oxide with dioxygen by a nonheme iron(II) complex.

J Biol Inorg Chem

School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A & 2B Raja S. C. Mullick Road, Jadavpur, Kolkata, 700032, India.

Published: February 2020

AI Article Synopsis

  • - Two iron(II) complexes, [(Tp)Fe(benzilate)] and [(Tp)(Fe)(NPP)], are studied for their ability to oxidize oximes in the presence of dioxygen, each following different mechanisms.
  • - The first complex, [(Tp)Fe(benzilate)], interacts with dioxygen to produce HNO from oximes, while the second complex, [(Tp)(Fe)(NPP)], transforms oximes into NO.
  • - The findings indicate that the oxidative transformation pathways to nitric oxide and nitroxyl depend on the type of co-ligand and reductant present in the reaction.

Article Abstract

The ability of two iron(II) complexes, [(Tp)Fe(benzilate)] (1) and [(Tp)(Fe)(NPP)] (2) (Tp = hydrotris(3,5-diphenylpyrazol-1-yl)borate, NPP-H = α-isonitrosopropiophenone), of a monoanionic facial N3 ligand in the O-dependent oxidation of oximes is reported. The mononuclear complex 1 reacts with dioxygen to decarboxylate the iron-coordinated benzilate. The oximate-bridged dinuclear complex (2), which contains a high-spin (Tp)Fe unit and a low-spin iron(II)-oximate unit, activates dioxygen at the high-spin iron(II) center. Both the complexes exhibit the oxidative transformation of oximes to the corresponding carbonyl compounds with the incorporation of one oxygen atom from dioxygen. In the oxidation process, the oxime units are converted to nitric oxide (NO) or nitroxyl (HNO). The iron(II)-benzilate complex (1) reacts with oximes to afford HNO, whereas the iron(II)-oximate complex (2) generates NO. The results described here suggest that the oxidative transformation of oximes to NO/HNO follows different pathways depending upon the nature of co-ligand/reductant.Graphic abstract.

Download full-text PDF

Source
http://dx.doi.org/10.1007/s00775-019-01726-6DOI Listing

Publication Analysis

Top Keywords

oxidation oximes
8
nitric oxide
8
complex reacts
8
oxidative transformation
8
transformation oximes
8
oximes
5
complex
5
bioinspired oxidation
4
oximes nitric
4
dioxygen
4

Similar Publications

Photocatalytic Partial Water Oxidation Promoted by a Hydrogen Acceptor-Hydroxyl Mediator Couple.

Adv Sci (Weinh)

December 2024

Soochow Institute for Energy and Materials InnovationS (SIEMIS), Soochow University, Suzhou, 215006, China.

Hydrogen peroxide (HO) is an important chemical in synthetic chemistry with huge demands. Photocatalytic synthesis of HO via oxygen reduction and water oxidation reactions (ORR and WOR) is considered as a promising and desirable solution for on-site applications. However, the efficiency of such a process is low due to the poor solubility of molecular oxygen and the rapid reverse reaction of hydroxyl radicals (OH) with hydrogen atoms (H).

View Article and Find Full Text PDF

Background/objectives: Alzheimer's disease (AD) is one of the most common neurodegenerative diseases, for which a definitive cure is still missing. Recently, natural compounds have been investigated for their possible neuroprotective role, including the bioactivated product of glucoraphanin (GRA), the sulforaphane (SFN), which is highly rich in cruciferous vegetables. It is known that SFN alleviates neuronal dysfunction, apoptosis, and oxidative stress in the brain.

View Article and Find Full Text PDF

Click chemistry has become one of the most powerful construction tools in the field of organic chemistry, materials science, and polymer science, as it offers hassle-free platforms for the high-yielding synthesis of novel materials and easy functionalization strategies. The absence of harsh reaction conditions or complicated workup procedures allowed the rapid development of novel biofunctional polymeric materials, such as biopolymers, tailor-made polymer surfaces, stimulus-responsive polymers, etc. In this review, we discuss various types of click reactions─including azide-alkyne cycloadditions, nucleophilic and radical thiol click reactions, a range of cycloadditions (Diels-Alder, tetrazole, nitrile oxide, etc.

View Article and Find Full Text PDF
Article Synopsis
  • * Three impurities, named 14-desmethyl-14-ethyl-MO A (1), 24-desmethyl-24-ethyl-MO A (2), and 12-desmethyl-12-ethyl-MO A (3), were successfully isolated and characterized through NMR analysis and ESIMS data.
  • * These impurities are newly identified isomers likely resulting from the oxidation and oximation of natural milbemycin homologs found in the fermentation process.
View Article and Find Full Text PDF

Acute Paraoxon-Induced Neurotoxicity in a Mouse Survival Model: Oxidative Stress, Dopaminergic System Alterations and Memory Deficits.

Int J Mol Sci

November 2024

Department of Pharmacology, Toxicology and Therapeutic Chemistry, Pharmacology Section and Institute of Biomedicine (IBUB), Faculty of Pharmacy, University of Barcelona, 08028 Barcelona, Spain.

Article Synopsis
  • The study investigates the secondary neurotoxicity resulting from severe organophosphorus (OP) poisoning, specifically paraoxon (POX), and its impact on cognitive functions in surviving mice.
  • Mice were injected with POX followed by various treatments, resulting in high survival rates but significant neurological changes such as increased lipid peroxidation and alterations in neurotransmitter levels in key brain areas linked to memory.
  • Despite no signs of depression or anxiety, the study found long-term memory impairments in the mice, highlighting the model's usefulness for exploring the effects of OP exposure and strategies to combat associated cognitive deficits.
View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!

A PHP Error was encountered

Severity: Notice

Message: fwrite(): Write of 34 bytes failed with errno=28 No space left on device

Filename: drivers/Session_files_driver.php

Line Number: 272

Backtrace:

A PHP Error was encountered

Severity: Warning

Message: session_write_close(): Failed to write session data using user defined save handler. (session.save_path: /var/lib/php/sessions)

Filename: Unknown

Line Number: 0

Backtrace: