Search results for "radical"
showing 10 items of 1401 documents
A Tale of Two Isomers: Enhanced Antiaromaticity/Diradical Character versus Deleterious Ring‐Opening of Benzofuran‐fused s ‐Indacenes and Dicyclopenta…
2021
We examine the effects of fusing two benzofurans to s-indacene (indacenodibenzofurans, IDBFs) and dicyclopenta[b,g]naphthalene (indenoindenodibenzofurans, IIDBFs) to control the strong antiaromaticity and diradical character of these core units. Synthesis via 3-functionalized benzofuran yields syn-IDBF and syn-IIDBF. syn-IDBF possesses a high degree of paratropicity, exceeding that of the parent hydrocarbon, which in turn results in strong diradical character for syn-IIDBF. In the case of the anti-isomers, synthesized via 2-substituted benzofurans, these effects are decreased; however, both derivatives undergo an unexpected ring-opening reaction during the final dearomatization step. All th…
Understanding the local reactivity in polar organic reactions through electrophilic and nucleophilic Parr functions
2013
[EN] Building upon our recent studies devoted to the bonding changes in polar reactions [RSC Advances, 2012, 2, 1334 and Org. Biomol. Chem., 2012, 10, 3841], we propose herein two new electrophilic, P-k(+), and nucleophilic, P-k(-), Parr functions based on the spin density distribution at the radical anion and at the radical cation of a neutral molecule. These local functions allow for the characterisation of the most electrophilic and nucleophilic centres of molecules, and for the establishment of the regio- and chemoselectivity in polar reactions. The proposed Parr functions are compared with both, the Parr-Yang Fukui functions [J. Am. Chem. Soc. 1984, 106, 4049] based on frontier molecul…
Electrochemical synthesis on boron-doped diamond
2012
Abstract Boron-doped diamond (BDD) is a novel and innovative electrode material. In protic media and particular aqueous electrolytes BDD exhibits a large over potential for the evolution of molecular hydrogen and oxygen. The large chemical window allows a variety of electrochemical conversions to be conducted. The anodic process treatment generates oxyl species directly which are known to be extremely reactive. Usually, the electrochemical mineralization of the organic components in the electrolyte occurs. However, with control of the reactivity of these intermediates the use in electroorganic synthesis can be realized. Until today mostly anodic conversions have been studied at BDD. Since h…
Tuning the Magnetic Properties of Carbon by Nitrogen Doping of Its Graphene Domains
2015
Here we present the formation of predominantly sp-coordinate carbon with magnetic- and heteroatom-induced structural defects in a graphene lattice by a stoichiometric dehalogenation of perchlorinated (hetero)aromatic precursors [hexachlorobenzene, CCl (HCB), and pentachloropyridine, NCCl (PCP)] with transition metals such as copper in a combustion synthesis. This route allows the build-up of a carbon lattice by a chemistry free of hydrogen and oxygen compared to other pyrolytic approaches and yields either nitrogen-doped or -undoped graphene domains depending on the precursor. The resulting carbon was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM…
Mass spectra of chlorinated aromatics formed in pulp bleaching: I—chlorinated catechols
1983
The fragmentation of chlorinated guaiacols (2-methoxyphenols) on electron impact has been studied. The most common fragmentation processes are interpreted and in some cases the small differences between spectra of positional isomers are explained. In addition to the well-known alkyl-oxygen fission (loss of methyl radical), metastable ion studies and deuterium labelling have indicated several new fragmentation pathways. The most characteristic are the formation of [MCH3HCl]+ and [MCH3Cl]+· ions. In general, however, the spectra of positional isomers are shown to be very similar.
Initial Radical Cation Pathway in the Mo2Cl10-Mediated Dehydrogenative Arene Coupling
2015
Experimental (EPR) and theoretical (DFT) evidence is provided for radical cation formation as initial step in the Mo2Cl10-mediated dehydrogenative arene coupling. The initial electron transfer from methoxyarenes to molybdenum proceeds via an inner sphere mechanism.
Die radikalausbeute beim thermischen zerfall von azoisobuttersäuredinitril in gegenwart von sauerstoff und in methylmethacrylat als lösungsmittel
1969
Die Radikalausbeute, gekennzeichnet durch den Radikalausbeutefaktor e (efficiency), beim thermischen Zerfall von Azoisobuttersauredinitril (AIBN) in sauerstoffhaltigen Losungen wurde mit Hilfe zweier direkter chemisch-analytischer Methoden bestimmt, die sich gegenseitig erganzen. Die 1. Methode beruht auf der gaschromatographischen Bestimmung des durch Kombination der primaren 2-Cyanoisopropylradikale entstehenden Tetramethylbernsteinsauredinitrils; sie liefert einen Wert fur (1-e). Die 2. Methode beruht auf der jodometrischen Bestimmung von 2-Cyanoisopropylhydroperoxid und p-Benzochinon, die letztlich durch eine Abfangreaktion mit Hydrochinon aus den der primaren Kombination entgangenen Ra…
Properties of methyl radical trapped in amorphous SiO2 and in natural SiO2-clathrate Melanophlogite
2013
Abstract We report an experimental investigation by electron paramagnetic resonance (EPR) on methyl radical (CH3 ) observed in γ-ray irradiated high-purity amorphous silicon dioxide (a-SiO2) and in a polycrystalline sample of Melanophlogite, a rare natural form of SiO2-clathrate. From the analysis of the EPR spectra we estimate the correlation time of the hindered rotational motion of CH3 molecules at T = 77 K in the two different materials. This physical quantity gives a quantitative measure of the freedom of motion of CH3 molecules trapped in the two solid systems, putting forward relevant information on the properties of the cavities/interstices in which the radicals are confined. In par…
Theoretical investigation of paramagnetic group 13 diazabutadiene radicals: insights into the prediction and interpretation of EPR spectroscopy param…
2006
The electronic structures and the spin density distributions of the group 13 1,4-diaza(1,3)butadiene (DAB) radicals [(R-DAB)2M]˙, [(R-DAB)MX2]˙ and {[(R-DAB)MX]2}˙˙ (M = Al, Ga, In; X = F, Cl, Br, I; R = H, Me, tBu, Ph) are studied using density functional theory at both non-relativistic and relativistic levels of theory. The calculations demonstrate that all systems share a qualitatively similar electronic structure and are primarily ligand centred π-radicals. The calculated metal, nitrogen and hydrogen hyperfine couplings are found to be independent of the identity of the R-group and the halogen atom. They are, however, dependent on the geometry and oxidation state of the metal centre. Bo…
Characterization of functional groups of airborne particulate matter
2013
Particulate matter of organic combustibles burning consists of various hydrocarbons and radicals, which may cause harmful impact to human health. In this study solid particulate matter were collected on the filters from burning of various combustibles in a burning chamber and from atmosphere of city of Riga by dichotomous impactor. FTIR spectra were obtained before and after samples' treatment. Absorptions associated with aliphatic and aromatic hydrocarbons and alcohol functional groups were observed in the FTIR spectra. Free radicals of particulate matter were detected by electron paramagnetic resonance (EPR).