Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

The Hydrates of TEMPO: Water Vibrations Reveal Radical Microsolvation.

ABSTRACT: An organic radical monohydrate complex is detected in vacuum isolation at low temperature by FTIR supersonic jet spectroscopy for the first time. It is shown to exhibit a rich conformational and vibrational coupling dynamics, which can be drastically reduced by appropriate isotope substitution. Its detection with a new gas recycling infrared spectrometer demonstrates the thermal metastability of the gaseous TEMPO radical even under humid gas conditions. Compared to its almost isoelectronic and isostructural, closed shell ketone analogue, the hydrogen bond of the solvating water is found to be less directional, but stronger and more strongly downshifting the bonded water OH stretch vibration. A second solvent water directs the first one into a metastable hydrogen bond position to solvate the nitrogen center and the first water at the same time.

SUBMITTER: Bras EM

PROVIDER: S-EPMC8456822 | biostudies-literature | 2021 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

The Hydrates of TEMPO: Water Vibrations Reveal Radical Microsolvation.

Brás Elisa M EM Fischer Taija L TL Suhm Martin A MA

Angewandte Chemie (International ed. in English) 20210728 35

An organic radical monohydrate complex is detected in vacuum isolation at low temperature by FTIR supersonic jet spectroscopy for the first time. It is shown to exhibit a rich conformational and vibrational coupling dynamics, which can be drastically reduced by appropriate isotope substitution. Its detection with a new gas recycling infrared spectrometer demonstrates the thermal metastability of the gaseous TEMPO radical even under humid gas conditions. Compared to its almost isoelectronic and i ...[more]

PMID: 34165885

Similar Datasets

Quantum Chemical Microsolvation by Automated Water Placement.

Project description:We developed a quantitative approach to quantum chemical microsolvation. Key in our methodology is the automatic placement of individual solvent molecules based on the free energy solvation thermodynamics derived from molecular dynamics (MD) simulations and grid inhomogeneous solvation theory (GIST). This protocol enabled us to rigorously define the number, position, and orientation of individual solvent molecules and to determine their interaction with the solute based on physical quantities. The generated solute-solvent clusters served as an input for subsequent quantum chemical investigations. We showcased the applicability, scope, and limitations of this computational approach for a number of small molecules, including urea, 2-aminobenzothiazole, (+)-syn-benzotriborneol, benzoic acid, and helicene. Our results show excellent agreement with the available ab initio molecular dynamics data and experimental results.

| S-EPMC8005176 | biostudies-literature

Interception of 1,2-cyclohexadiene with TEMPO radical.

Project description:Transient strained cyclic intermediates, such as strained cyclic allenes, are useful building blocks for the synthesis of structurally and stereochemically complex scaffolds. Trappings of strained cyclic allenes are thought to occur primarily through either two or one electron processes. Regarding the latter, diradical intermediates have been invoked in (2 + 2) cycloadditions and (3 + 2) nitrone cycloadditions. The present study questions if a monoradical pathway could exist for strained cyclic allene reactivity, as examined in the reaction of 1,2-cyclohexadiene and TEMPO radical. Our findings suggest the viability of this monoradical pathway.

| S-EPMC8699062 | biostudies-literature

Intermolecular radical oxyalkylation of arynes with alkenes and TEMPO.

Project description:Radical transformations with arynes represent an underexplored research field and only a few examples have been disclosed. In this research article, the implementation of arynes in three-component reactions with TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) and activated alkenes is demonstrated. TEMPO is added to arynes, which triggers a Meerwein-type arylation cascade where the final alkyl radial is eventually trapped by a second equivalent of TEMPO. This method is applicable to activated alkenes such as electron-deficient acrylates, styrenes and also vinyl acetate to provide various bisalkoxyamines. This work is a contribution to the emerging field of radical aryne chemistry.

| S-EPMC11351772 | biostudies-literature

Allene Trifunctionalization <i>via</i> Amidyl Radical Cyclization and TEMPO Trapping.

Project description:Radical-mediated trifunctionalizations of allenes are virtually unknown, in contrast to well-studied radical difunctionalizations of alkenes and alkynes. In this article, we describe a light-promoted reaction that transforms all three allene carbons to new carbon-heteroatom bonds in one pot with no expensive transition-metal catalyst. Formation of an electron donor-acceptor complex between an electron-deficient aryl and K2CO3, followed by photochemical generation of an amidyl radical and cyclization, yields a vinyl radical that can be trapped by TEMPO to ultimately furnish the product. Insights into the impact of the allene substitution pattern, radical source, and donor are presented, along with studies to unravel the mechanism of this unusual transformation.

| S-EPMC8290888 | biostudies-literature

Rapid Water Softening with TEMPO-Oxidized/Phosphorylated Nanopapers.

Project description:Water hardness not only constitutes a significant hazard for the functionality of water infrastructure but is also associated with health concerns. Commonly, water hardness is tackled with synthetic ion-exchange resins or membranes that have the drawbacks of requiring the awkward disposal of saturated materials and being based on fossil resources. In this work, we present a renewable nanopaper for the purpose of water softening prepared from phosphorylated TEMPO-oxidized cellulose nanofibrils (PT-CNF). Nanopapers were prepared from CNF suspensions in water (PT-CNF nanopapers) or low surface tension organic liquids (ethanol), named EPT-CNF nanopapers, respectively. Nanopaper preparation from ethanol resulted in a significantly increased porosity of the nanopapers enabling much higher permeances: more than 10,000× higher as compared to nanopapers from aqueous suspensions. The adsorption capacity for Ca2+ of nanopapers from aqueous suspensions was 17 mg g-1 and 5 mg g-1 for Mg2+; however, EPT-CNF nanopapers adsorbed more than 90 mg g-1 Ca2+ and almost 70 mg g-1 Mg2+. The higher adsorption capacity was a result of the increased accessibility of functional groups in the bulk of the nanopapers caused by the higher porosity of nanopapers prepared from ethanol. The combination of very high permeance and adsorption capacity constitutes a high overall performance of these nanopapers in water softening applications.

| S-EPMC6409817 | biostudies-literature

Arynes as Radical Acceptors: TEMPO-Mediated Cascades Comprising Addition, Cyclization, and Trapping.

Project description:The application of arynes as radical acceptors is described. The stable radical TEMPO (2,2,6,6-tetramethyl piperidine 1-oxyl) is shown to add to various ortho-substituted benzynes generating the corresponding aryl radicals which engage in 5-exo or 6-endo cyclizations. The cyclized radicals are eventually trapped by TEMPO. The introduced method provides ready access to various dihydrobenzofurans, oxindoles, and sultones by a conceptually novel approach.

| S-EPMC7839731 | biostudies-literature

Effect of Water Microsolvation on the Excited-State Proton Transfer of 3-Hydroxyflavone Enclosed in ?-Cyclodextrin.

Project description:The effect of microsolvation on excited-state proton transfer (ESPT) reaction of 3-hydroxyflavone (3HF) and its inclusion complex with ?-cyclodextrin (?-CD) was studied using computational approaches. From molecular dynamics simulations, two possible inclusion complexes formed by the chromone ring (C-ring, Form I) and the phenyl ring (P-ring, Form II) of 3HF insertion to ?-CD were observed. Form II is likely more stable because of lower fluctuation of 3HF inside the hydrophobic cavity and lower water accessibility to the encapsulated 3HF. Next, the conformation analysis of these models in the ground (S0) and the first excited (S1) states was carried out by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations, respectively, to reveal the photophysical properties of 3HF influenced by the ?-CD. The results show that the intermolecular hydrogen bonding (interHB) between 3HF and ?-CD, and intramolecular hydrogen bonding (intraHB) within 3HF are strengthened in the S1 state confirmed by the shorter interHB and intraHB distances and the red-shift of O-H vibrational modes involving in the ESPT process. The simulated absorption and emission spectra are in good agreement with the experimental data. Significantly, in the S1 state, the keto form of 3HF is stabilized by ?-CD, explaining the increased quantum yield of keto emission of 3HF when complexing with ?-CD in the experiment. In the other word, ESPT of 3HF is more favorable in the ?-CD hydrophobic cavity than in aqueous solution.

| S-EPMC7914428 | biostudies-literature

High-pressure preference for reduced water content in porous zinc aspartate hydrates.

Project description:The zinc aspartate (ZnAsp2) complex, a common dietary supplement, preferentially crystallizes as the dihydrate (ZnAsp2·2H2O) from aqueous solution. Under normal conditions the dihydrate easily transforms into the sesquihydrate (ZnAsp2·1.5H2O). The dihydrate crystal structure is triclinic, space group P1, and the sesquihydrate is monoclinic, space group C2/c. However, their structures are closely related and similarly consist of zinc aspartate ribbons parallel to pores accommodating water molecules. These porous structures can breathe water molecules in and out depending on the temperature and air humidity. High pressure above 50 MPa favours the sesquihydrate, as shown by recrystallizations under pressure and compressibility measured by single-crystal X-ray diffraction up to 4 GPa. This preference is explained by the reduced volume of the sesquihydrate and water compressed separately, compared with the dihydrate. The sesquihydrate undergoes an isostructural phase transition when the voids collapse at 0.8 GPa, whereas no phase transitions occur in the dihydrate, because its pores are supported by increased water content.

| S-EPMC7535066 | biostudies-literature

Mechanochemical and slow-chemistry radical transformations: a case of diorganozinc compounds and TEMPO.

Project description:From the green chemistry perspective, molecular solid-state transformations conducted under mild conditions are of great interest and desirability. However, research in this area lacked popularity in the previous century, and thus progressed slowly. In particular, the application of radical reactions in solid-state chemistry has been hampered by several long-standing challenges that are intrinsically associated with the apparent unpredictable nature of radical chemistry. We present a comparative study of model mechanochemical, slow-chemistry and solution radical reactions between TEMPO and homoleptic organozinc compounds (i.e., di-tert-butylzinc and diphenylzinc). In the case of the tBu2Zn/TEMPO reaction system only a dimeric diamagnetic complex [tBuZn(μ-TEMPO*)]2 is obtained in yields slightly varying with the method chosen. In contrast, when TEMPO is mixed with diphenylzinc in a 2 : 1 molar ratio a novel paramagnetic Lewis acid-base adduct [[Ph2Zn(η1-TEMPO)]·TEMPO] is isolated in high yields regardless of the applied methodology. This adduct is also formed in the slow-chemistry process when TEMPO is gently mixed with Ph2Zn in a 1 : 1 molar ratio and left for two weeks at ambient temperature. Within the next week the reaction mixture gives in high yield a diamagnetic dinuclear compound [PhZn(μ-TEMPO*)][PhZn(μ2-η1:η1-TEMPO*)] and biphenyl. The analogous reaction conducted in toluene results in a much lower conversion rate. The reported results open up a new horizon in molecular solid-state radical transformations.

| S-EPMC6686643 | biostudies-literature

Redox-Neutral TEMPO Catalysis: Direct Radical (Hetero)Aryl C-H Di- and Trifluoromethoxylation.

Project description:Applications of TEMPO. catalysis for the development of redox-neutral transformations are rare. Reported here is the first TEMPO. -catalyzed, redox-neutral C-H di- and trifluoromethoxylation of (hetero)arenes. The reaction exhibits a broad substrate scope, has high functional-group tolerance, and can be employed for the late-stage functionalization of complex druglike molecules. Kinetic measurements, isolation and resubjection of catalytic intermediates, UV/Vis studies, and DFT calculations support the proposed oxidative TEMPO. /TEMPO+ redox catalytic cycle. Mechanistic studies also suggest that Li2 CO3 plays an important role in preventing catalyst deactivation. These findings will provide new insights into the design and development of novel reactions through redox-neutral TEMPO. catalysis.

| S-EPMC7720849 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data