A5034980386- Chemical Reactions and Mechanisms
- Oxidative Organic Chemistry Reactions
- Catalysis and Oxidation Reactions
- Advanced oxidation water treatment
- Atmospheric chemistry and aerosols
- Atmospheric Ozone and Climate
- Chemical Reaction Mechanisms
- Electron Spin Resonance Studies
- Advanced Chemical Physics Studies
- Photochemistry and Electron Transfer Studies
- Fullerene Chemistry and Applications
- Surfactants and Colloidal Systems
- Crystallization and Solubility Studies
- Spectroscopy and Quantum Chemical Studies
- Organic Chemistry Cycloaddition Reactions
- Asymmetric Synthesis and Catalysis
- Spectroscopy and Laser Applications
- X-ray Diffraction in Crystallography
- Chemical Synthesis and Reactions
- Water Quality Monitoring and Analysis
- Catalytic Processes in Materials Science
- Inorganic and Organometallic Chemistry
- Polyoxometalates: Synthesis and Applications
- Molecular Spectroscopy and Structure
- Free Radicals and Antioxidants
University of Ljubljana
2011-2025
University of Strathclyde
2008-2010
National Institute of Chemistry
2009
University of the Pacific
2006
Hydrogen-bonded cocrystals have attracted considerable attention as they allow fine-tuning of properties through the choice hydrogen-bond donors and acceptors. In this study, triphenylarsine oxide (Ph3AsO) is introduced a strong acceptor molecule. Due to its higher Lewis basicity compared triphenylphosphine (Ph3PO), it acts acceptor, which demonstrated in six new with H2O2 gem-di(hydroperoxy)cycloalkanes. All formed large, high-quality single crystals, were analyzed by X-ray diffraction IR...
A bigger mechanistic picture of electrophilic aromatic substitution (EAS) is summarized and important “missing” postulates in EAS are unified.
Low-temperature ozonation of cumene (1a) in acetone, methyl acetate, and tert-butyl ether at −70° C produced the corresponding hydrotrioxide, C6H5C(CH3)2OOOH (2a), along with hydrogen trioxide, HOOOH. Ozonation triphenylmethane (1b), however, only triphenylmethyl (C6H5)3COOOH (2b). These observations, together previously reported experimental evidence, seem to support "radical" mechanism for first step C−H bonds hydrocarbons, i.e., formation caged radical pair (R• •OOOH), which allows both...
Ozonation of various silanes and germanes produced the corresponding hydrotrioxides, R3SiOOOH R3GeOOOH, which were characterized by 1H, 13C, 17O, 29Si NMR, infrared spectroscopy in a two-pronged approach based on measured calculated data. Ozone reacts with E−H (E = Si, Ge) bond via concerted 1,3-dipolar insertion mechanism, where, depending substituents environment (e.g., acetone-d6 solution), H atom transfer precedes more E−O formation. The hydrotrioxides decompose solvents into...
Low-temperature (−78 °C) ozonation of 1,2-diphenylhydrazine in various oxygen bases as solvents (acetone-d6, methyl acetate, tert-butyl ether) produced hydrogen trioxide (HOOOH), 1,2-diphenyldiazene, 1,2-diphenyldiazene-N-oxide, and peroxide. Ozonation 1,2-dimethylhydrazine besides HOOOH, 1,2-dimethyldiazene, 1,2-dimethyldiazene-N-oxide peroxide, also formic acid nitromethane. Kinetic activation parameters for the decomposition HOOOH this way, identified by 1H, 2H, 17O NMR spectroscopy, are...
Low-temperature ozonation of isopropyl alcohol (1a) and methyl ether (1b) in [D6]acetone, acetate, tert-butyl at -78 degrees C produced the corresponding hydrotrioxides, Me2C(OH)(OOOH) (2a) Me2C(OMe)(OOOH) (2b), along with hydrogen trioxide (HOOOH). All polyoxides investigated were characterized for first time by 17O NMR spectroscopy highly 17O-enriched species. The assignment was confirmed GIAO/MP2/6-31++G* calculations chemical shifts, which excellent agreement experimental values. Ab...
ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTOn the Mechanism of Ozonation Isopropyl Alcohol: An Experimental and Density Functional Theoretical Investigation. 17O NMR Spectra Hydrogen Trioxide (HOOOH) Hydrotrioxide AlcoholBožo Plesničar, Janez Cerkovnik, Tomaž Tekavec, Jože KollerView Author Information Department Chemistry University Ljubljana P.O. Box 537, 1000 Ljubljana, Slovenia Cite this: J. Am. Chem. Soc. 1998, 120, 31, 8005–8006Publication Date (Web):July 28, 1998Publication...
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCharacterization and reactivity of hydrogen trioxide (HOOOH), a reactive intermediate formed in the low-temperature ozonation 2-ethylanthrahydroquinoneJanez Cerkovnik Bozo PlesnicarCite this: J. Am. Chem. Soc. 1993, 115, 25, 12169–12170Publication Date (Print):December 1, 1993Publication History Published online1 May 2002Published inissue 1 December...
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTChemistry of hydrotrioxides. Preparation, characterization, and reactivity dimethylphenylsilyl Hydrogen trioxide (HOOOH), a reactive intermediate in their thermal decomposition?Bozo Plesnicar, Janez Cerkovnik, Joze Koller, Franci KovacCite this: J. Am. Chem. Soc. 1991, 113, 13, 4946–4953Publication Date (Print):June 1, 1991Publication History Published online1 May 2002Published inissue 1 June...
Low-temperature ozonation (−78 °C) of 2-methyl-1,3-dioxolane (1a) in acetone-d6, methyl acetate, and tert-butyl ether produced both the corresponding acetal hydrotrioxide (3a, ROOOH) hemiortho ester (2a, ROH) molar ratio 1:5. Both intermediates were fully characterized by 1H, 13C, 17O NMR spectroscopy, they decomposed to hydroxy at higher temperatures. The mechanism involving HOOO- anion formed abstraction hydride ion ozone form an pair, R+ -OOOH, with its subsequent collapse either (ROH) or...
Low-temperature ozonation (-78 degrees C) of 1,3-dioxolanes 1a-1f and 1,3-dioxanes 1g h in acetone-d6, methyl acetate, tert-butyl ether produced both the corresponding hemiortho esters (2a-h, ROH) acetal hydrotrioxides (3a-h, ROOOH) molar ratios ROH/ROOOH ranging from 0.5 to 23. Both types intermediates were fully characterized by 1H, 13C, 17O NMR spectroscopy. DFT calculations suggest that ozone abstracts a hydride ion 1 form an pair, R+ -OOOH, which subsequently collapses either ester...
Hydrogen-bonded gas-phase molecular clusters of dihydrogen trioxide (HOOOH) have been investigated using DFT (B3LYP/6-311++G(3df,3pd)) and MP2/6-311++G(3df,3pd) methods. The binding energies, vibrational frequencies, dipole moments for the various dimer, trimer, tetramer structures, in which HOOOH acts as a proton donor well an acceptor, are reported. stronger interaction compared to that analogous cyclic structure HOOH indicates is acid than hydrogen peroxide. A new decomposition pathway...
The behavior of poly(alpha-ethylacrylic acid), PEA, was studied in aqueous solutions at 25 degrees C and a polymer concentration 0.01 mol carboxyl groups/L by conductometric, potentiometric, calorimetric, fluorescence measurements. PEA chains were characterized for molar mass, eventual crystallinity, tacticity. complete thermodynamic characterization the transition from contracted to an expanded form is reported. results show that short are strongly associated water. Intermolecular...
Dihydrogen trioxide (HOOOH) is formed nearly quantitatively in the low-temperature (-70 degrees C) methyltrioxorhenium(VII) (MTO)-catalyzed transformation of silyl hydrotrioxides (R3SiOOOH), and some acetal hydrotrioxides, various solvents, as confirmed by 1H, 17O NMR spectroscopy. The calculated energetics (B3LYP) for catalytic cycle, using H3SiOOOH a model system, consistent with experimentally observed activation energy (9.5 +/- 2.0 kcal/mol) small kinetic solvent isotope effect...
We demonstrate in this work by theory and experiment that benzaldehyde hydrotrioxide (PhC(O)OOOH), the intermediate most likely formed low-temperature ozonation of benzaldehyde, is too unstable to be detected NMR (1H, 13C, 17O) spectroscopy various organic solvents at temperatures ≥ −80 °C its previous detection must have been erroneous. Several plausible mechanisms for formation polyoxide were explored using density functional theory. found involves facile 1,3-dipolar insertion ozone into...
The capability of ozone to reduce the hazardous impact environmentally persistent antibiotic tiamulin in term toxicity reduction and enhancement biodegradability was investigated. Different doses were applied but ozonation not effective enough increase aqueous phase. opposite effect observed anaerobic digestion experiments, where as a pretreatment step antibiotic-contaminated sludge detoxify improves biogas production for 75%. As confirmed by 1H NMR HPLC-HRMS analyses, molecule completely...
Following the procedure given in literature, we prepared water-soluble Th symmetric derivative of fullerene C60, at which six malonic acid molecules have been attached, Th-C60(C(COOH)2)6. The sample has characterized by some fundamental physicochemical data and properties: 13C NMR chemical shifts for its sodium salt, solubility data, potentiometric conductometric titration curves, electrical conductivity, osmotic coefficient, apparent molar volume. It found that fullerenehexamalonic (FHMA),...
Protonated dihydrogen trioxide (HOOOH) has been postulated in various forms for many years. Protonation can occur at either the terminal (HOOO(H)H(+)) or central (HOOH(OH)(+)) oxygen atom. However, to date there no definitive evidence provided of these species. In current work we have employed ab initio methods, CCSD(T) and MP2, with a large basis set (6-311++G(3df,3pd)) determine relative stabilities It is shown that terminally protonated species strongly favored centrally (DeltaE = 15.8...