2-Benzylindane radical cations in the gas phase (Part I): Substituent effects on a stereoselective McLafferty reaction and related hydrogen transfer processes

2017 ◽  
Vol 413 ◽  
pp. 106-116 ◽  
Author(s):  
Hans-Friedrich Grützmacher ◽  
Dietmar Kuck
Keyword(s):  
Gas Phase ◽  
Hydrogen Transfer ◽  
Substituent Effects ◽  
Radical Cations ◽  
Transfer Processes

Electrostatic effects on ionization equilibria: An MNDO study of proton and hydrogen transfer reactions of 4-fluorobutylamine

1990 ◽  
Vol 55 (1) ◽  
pp. 1-9 ◽  
Author(s):  
Zdeněk Friedl ◽  
Stanislav Böhm
Keyword(s):  
Hydrogen Transfer ◽  
Substituent Effects ◽  
Radical Cations ◽  
Transfer Reactions ◽  
Protonated Forms ◽  
Minor Part ◽  
Bond Strengths ◽  
Ionization Equilibria ◽  
A Minor ◽  
Gas Phase Basicities

The relative enthalpies of proton transfer δ ΔH0and homolytic bond strengths δDH0(B-H+) were calculated by the MNDO method for the sp and ap conformers of 4-flurobutylamine. The data obtained, along with the experimental gas phase basicities, are compared with the values predicted by the electrostatic theory. It is shown that the substituent polar effects FD on the basicities of amines are predominantly due to interactions in their protonated forms (X-B-H+) and/or radical-cations (X-B+.), those in the neutral species (X-B) playing a minor part. A contribution, which is considerably more significant in the sp conformer than in the ap conformer, arises probably also from substituent effects on the homolytic bond strength DH0(B-H+.

Electrostatic effects on ionization equilibria: MNDO study of proton and hydrogen transfer reactions of 5-fluoropentanoic acid

1985 ◽  
Vol 63 (5) ◽  
pp. 1068-1072 ◽  
Author(s):  
Zdenek Friedl
Keyword(s):  
Proton Transfer ◽  
Gas Phase ◽  
Carboxylic Acids ◽  
Hydrogen Transfer ◽  
Opposite Sign ◽  
Substituent Effects ◽  
Transfer Reactions ◽  
Small Contribution ◽  
Bond Strengths ◽  
Ionization Equilibria

Relative proton transfer enthalpies δΔH0 and homolytic bond strengths δΔH0 (A—H) of sp and ap conformers of 5-fluoropentanoic acid, as well as some related aliphatic and 4-X-bicyclo[2.2.2]octane-1-carboxylic halogenoacids, have been calculated by the MNDO method. The results, together with literature data concerning the gas phase acidities, were compared with the prediction of the electrostatic theory. It is shown that the substituent effects on acidities of carboxylic acids are largely due to substituent interactions in the anions and only to a smaller extent to interactions in the neutral acids. A small contribution (about one-eighth to one-fourth as large in magnitude but of opposite sign) is possibly also made by substituent effects on homolytic bond strengths DH0 (A—H).

Effect of Niacin on Mitochondria of Allium Cepa Root Cells

1967 ◽  
Vol 25 ◽  
pp. 78-79
Author(s):  
M. Arif Hayat
Keyword(s):  
Nicotinamide Adenine Dinucleotide ◽  
Hydrogen Transfer ◽  
Nicotinamide Adenine Dinucleotide Phosphate ◽  
Nicotinamide Adenine ◽  
Root Tips ◽  
Root Cells ◽  
Transfer Processes ◽  
Standard Procedures ◽  
A Cell ◽  
Critical Interest

Although it is recognized that niacin (pyridine-3-carboxylic acid), incorporated as the amide in nicotinamide adenine dinucleotide (NAD) or in nicotinamide adenine dinucleotide phosphate (NADP), is a cofactor in hydrogen transfer in numerous enzyme reactions in all organisms studied, virtually no information is available on the effect of this vitamin on a cell at the submicroscopic level. Since mitochondria act as sites for many hydrogen transfer processes, the possible response of mitochondria to niacin treatment is, therefore, of critical interest.Onion bulbs were placed on vials filled with double distilled water in the dark at 25°C. After two days the bulbs and newly developed root system were transferred to vials containing 0.1% niacin. Root tips were collected at ¼, ½, 1, 2, 4, and 8 hr. intervals after treatment. The tissues were fixed in glutaraldehyde-OsO4 as well as in 2% KMnO4 according to standard procedures. In both cases, the tissues were dehydrated in an acetone series and embedded in Reynolds' lead citrate for 3-10 minutes.

Reactivity Trends in the Gas Phase Addition of Acetylene to N-protonated Aryl Radical Cations

2020 ◽  
Author(s):  
Oisin Shiels ◽  
P. D. Kelly ◽  
Cameron C. Bright ◽  
Berwyck L. J. Poad ◽  
Stephen Blanksby ◽  
...  
Keyword(s):  
Gas Phase ◽  
Ion Trap ◽  
Radical Cations ◽  
Rate Coefficients ◽  
Similar Process ◽  
Ion Molecule Reactions ◽  
Aromatic Radicals ◽  
Polycyclic Aromatic ◽  
Gas Phase Ion ◽  
Type Radical

<div> <div> <div> <p>A key step in gas-phase polycyclic aromatic hydrocarbon (PAH) formation involves the addition of acetylene (or other alkyne) to σ-type aromatic radicals, with successive additions yielding more complex PAHs. A similar process can happen for N- containing aromatics. In cold diffuse environments, such as the interstellar medium, rates of radical addition may be enhanced when the σ-type radical is charged. This paper investigates the gas-phase ion-molecule reactions of acetylene with nine aromatic distonic σ-type radical cations derived from pyridinium (Pyr), anilinium (Anl) and benzonitrilium (Bzn) ions. Three isomers are studied in each case (radical sites at the ortho, meta and para positions). Using a room temperature ion trap, second-order rate coefficients, product branching ratios and reaction efficiencies are reported. </p> </div> </div> </div>

scholarly journals Substituent Effects on EI-MS Fragmentation Patterns of 5-Allyloxy-1-aryl-tetrazoles and 4-Allyl-1-aryl-tetrazole-5-ones; Correlation with UV-Induced Fragmentation Channels

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3282
Author(s):  
Alina Secrieru ◽  
Rabah Oumeddour ◽  
Maria L. S. Cristiano
Keyword(s):  
Theoretical Calculations ◽  
Substituent Effects ◽  
Radical Cations ◽  
Electronic Effects ◽  
Diverse Range ◽  
The Matrix ◽  
Electron Impact Mass ◽  
Fragmentation Patterns ◽  
Tetrazole Derivatives ◽  
Impact Mass

1,4- and 1,5-disubstituted tetrazoles possess enriched structures and versatile chemistry, representing a challenge for chemists. In the present work, we unravel the fragmentation patterns of a chemically diverse range of 5-allyloxy-1-aryl-tetrazoles and 4-allyl-1-aryl-tetrazolole-5-ones when subjected to electron impact mass spectrometry (EI-MS) and investigate the correlation with the UV-induced fragmentation channels of the matrix-isolated tetrazole derivatives. Our results indicate that the fragmentation pathways of the selected tetrazoles in EI-MS are highly influenced by the electronic effects induced by substitution. Multiple pathways can be envisaged to explain the mechanisms of fragmentation, frequently awarding common final species, namely arylisocyanate, arylazide, arylnitrene, isocyanic acid and hydrogen azide radical cations, as well as allyl/aryl cations. The identified fragments are consistent with those found in previous investigations concerning the photochemical stability of the same class of molecules. This parallelism showcases a similarity in the behaviour of tetrazoles under EI-MS and UV-irradiation in the inert environment of cryogenic matrices of noble gases, providing efficient tools for reactivity predictions, whether for analytical ends or more in-depth studies. Theoretical calculations provide complementary information to articulate predictions of resulting products.

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