Gas-Phase Acidities of Acetophenone Oximes. Substituent Effect and Solvent Effects

Md. Mizanur Rahman Badal; Masaaki Mishima

doi:10.1246/bcsj.20090246

Solvent and temperature effects on the tautomerization of a carbonitrile molecule: A conductor-like polarizable continuum model (CPCM) study

Main Group Chemistry ◽

10.3233/mgc-210016 ◽

2021 ◽

Vol 20 (1) ◽

pp. 59-68

Author(s):

Zohreh Khanjari ◽

Bita Mohtat ◽

Reza Ghiasi ◽

Hoorieh Djahaniani ◽

Farahnaz Kargar Behbahani

Keyword(s):

Gas Phase ◽

Solvent Effects ◽

Continuum Model ◽

Solvent Polarity ◽

Polarizable Continuum Model ◽

Dielectric Constants ◽

Frontier Orbitals ◽

Reaction Field ◽

Polarizable Continuum ◽

Homo Lumo

This research examined the effects of solvent polarity and temperature on the tautomerization of a carbonitrile molecule at CAM-B3LYP/6-311G (d,p) level of theory. The selected solvents were n-hexane, diethyl ether, pyridine, ethanol, methanol, and water. The solvent effects were examined by the self-consistent reaction field theory (SCRF) based on conductor-like polarizable continuum model (CPCM). The solvent effects were explored on the energy barrier, frontier orbitals energies, and HOMO-LUMO gap. Dependencies of thermodynamic parameters (ΔG and ΔH) on the dielectric constants of solvents were also tested. Specifically, the temperature dependencies of the thermodynamics parameters were studied within 100–1000 K range. The rate constant of the tautomerism reaction was computed from 300 to 1200 K, in the gas phase.

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ChemInform Abstract: Aromatic Substituent Effect on the Stereoselectivity of the Condensed- and Gas-Phase Acid-Induced Methanolysis in 2-Aryloxiranes Derived from 3,4-Dihydronaphthalene and trans-1,2,3,4,4a,10a-Hexahydrophenanthrene Bearing a Tertiary Ben

ChemInform ◽

10.1002/chin.199730100 ◽

2010 ◽

Vol 28 (30) ◽

pp. no-no

Author(s):

P. CROTTI ◽

V. DI BUSSOLO ◽

L. FAVERO ◽

M. PINESCHI ◽

D. SERGIAMPIETRI ◽

...

Keyword(s):

Gas Phase ◽

Substituent Effect ◽

Aromatic Substituent

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Substituent effect on electron affinity, gas-phase basicity, and structure of monosubstituted propargyl radicals and their anions: a theoretical study

Journal of Physical Organic Chemistry ◽

10.1002/poc.1579 ◽

2009 ◽

pp. n/a-n/a

Author(s):

Gab-Yong Lee

Keyword(s):

Gas Phase ◽

Electron Affinity ◽

Substituent Effect ◽

Theoretical Study ◽

Propargyl Radicals

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Solvent effects on the electrical and magnetic spectroscopic properties of azo-enaminone derivatives in methanol and in water

New Journal of Chemistry ◽

10.1039/c8nj01842a ◽

2018 ◽

Vol 42 (14) ◽

pp. 12032-12044 ◽

Cited By ~ 1

Author(s):

Leonardo Bruno Assis Oliveira ◽

Luizmar Adriano Júnior ◽

Guilherme Colherinhas

Keyword(s):

Optical Properties ◽

Gas Phase ◽

Solvent Effects ◽

Spectroscopic Properties ◽

Water Solutions

We have investigated the solvent effects on the nonlinear and spectroscopic optical properties of some azo-enaminone molecules in the gas phase and in methanol and water solutions.

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AbInitio SCF MO calculations on the reaction of hydroxyl radical with cytosine

Canadian Journal of Chemistry ◽

10.1139/v86-151 ◽

1986 ◽

Vol 64 (5) ◽

pp. 914-919 ◽

Cited By ~ 3

Author(s):

Beverley G. Eatock ◽

William L. Waltz ◽

Paul G. Mezey

Keyword(s):

Hydroxyl Radical ◽

Radiation Damage ◽

Gas Phase ◽

Solvent Effects ◽

Oh Radical ◽

Mo Calculations ◽

Relative Stabilities ◽

Ring Atom ◽

Living Tissues ◽

Abinitio Calculations

Abinitio calculations have been carried out on the relative stabilities of various possible products of the reaction between cytosine and the OH radical. These products are of importance in modelling radiation damage to living tissues. The preferred theoretical gas-phase addition site is the C6 ring atom according to these calculations. The analysis of a series of possible contributions to solvent effects strongly suggests the predominance of intermolecular H bonds in stabilizing the experimentally observed C5 adduct.

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ChemInform Abstract: Solvent Effects on the NMR Shieldings of Nitrogen Atoms in Azole and Azine Systems: Their Counterparts in the Gas Phase

ChemInform ◽

10.1002/chin.200140030 ◽

2010 ◽

Vol 32 (40) ◽

pp. no-no

Author(s):

J. Catalan

Keyword(s):

Gas Phase ◽

Solvent Effects

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Bond-dissociation enthalpies in the gas phase and in organic solvents: Making ends meet

Pure and Applied Chemistry ◽

10.1351/pac200779081369 ◽

2007 ◽

Vol 79 (8) ◽

pp. 1369-1382 ◽

Cited By ~ 8

Author(s):

Rui M. Borges dos Santos ◽

Benedito J. Costa Cabral ◽

José A. Martinho Simões

Keyword(s):

Gas Phase ◽

Organic Solvents ◽

Solvent Effects ◽

Solution Phase ◽

Parent Molecule ◽

Solvent Interaction ◽

Solvation Effects ◽

Bond Dissociation ◽

The Difference

Solvent effects are responsible for the difference between gas- and solution-phase bond-dissociation enthalpies (BDEs), and are thus crucial for understanding reactivity in solution. While solvation effects can be negligible (e.g., in reactions involving carbon-centered radicals), they may be rather significant (e.g., when oxygen-centered radicals are formed). This paper reviews a number of models which have been proposed to deal with the difference between the solvation energetics of a radical and its parent molecule. It is concluded that the radical-solvent interaction may be larger than previously anticipated.

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