Solvent Effects on the Energetics of the Phenol O-H Bond: Differential Solvation of Phenol and Phenoxy Radical in Benzene and Acetonitrile
نویسندگان
چکیده
Departamento de Quı́mica e Bioquı́mica, Faculdade de Ciências da UniVersidade de Lisboa, 1749-016 Lisboa, Portugal, Grupo de Fı́sica Matemática da UniVersidade de Lisboa, AV. Professor Gama Pinto 2, 1649-003 Lisboa, Portugal, UniVersidade de Mogi das Cruzes, CP 411, 08701-970 Mogi das Cruzes, São Paulo, Brazil, Instituto de Fı́sica, UniVersidade de São Paulo, CP 66318, 05315-970 São Paulo, São Paulo, Brazil, and Faculdade de Engenharia de Recursos Naturais, UniVersidade do AlgarVe, Campus de Gambelas, 8005-139 Faro, Portugal
منابع مشابه
Kinetic solvent effects on hydrogen abstraction from phenol by the cumyloxyl radical. Toward an understanding of the role of protic solvents.
A time-resolved kinetic study of the hydrogen atom abstraction reactions from phenol by the cumyloxyl radical (CumO(•)) was carried out in different solvents. The hydrogen atom abstraction rate constant (k(H)) was observed to decrease by almost 3 orders of magnitude on going from isooctane to MeOH. In TFE, MeCN/H(2)O 2:1, and MeOH, the measured k(H) values were lower than expected on the basis ...
متن کاملInvestigation of solute-solvent interactions in phenol compounds: accurate ab initio calculations of solvent effects on 1H NMR chemical shifts.
Accurate (1)H chemical shifts of the -OH groups of polyphenol compounds can be calculated, compared to experimental values, using a combination of DFT, polarizable continuum model (PCM) and discrete solute-solvent hydrogen bond interactions. The study focuses on three molecular solutes: phenol, 4-methylcatechol and the natural product genkwanin in DMSO, acetone, acetonitrile, and chloroform. Ex...
متن کاملHydrogen bond lifetimes and energetics for solute/solvent complexes studied with 2D-IR vibrational echo spectroscopy.
Weak pi hydrogen-bonded solute/solvent complexes are studied with ultrafast two-dimensional infrared (2D-IR) vibrational echo chemical exchange spectroscopy, temperature-dependent IR absorption spectroscopy, and density functional theory calculations. Eight solute/solvent complexes composed of a number of phenol derivatives and various benzene derivatives are investigated. The complexes are for...
متن کاملDirect Oxidation of Benzene to Phenol in Liquid Phase over Nanoporous Silica of Chromium-LUS-1
(Received: May 18, 2012; Accepted in Revised Form: February 4, 2013) Abstract: Direct oxidation of benzene to phenol in liquid phase in the medium of methanol, acetone, acetic acid and acetonitrile as a solvent over chromium catalyst supported on highly ordered nanoporous silica (Cr-LUS-1) by H O were examined. The best results obtained from methanol solvent with 20% yield and selectivity of 90...
متن کاملProducts of the benzene + O(3P) reaction.
The gas-phase reaction of benzene with O((3)P) is of considerable interest for modeling of aromatic oxidation, and also because there exist fundamental questions concerning the prominence of intersystem crossing in the reaction. While its overall rate constant has been studied extensively, there are still significant uncertainties in the product distribution. The reaction proceeds mainly throug...
متن کامل