A contribution to mechanism of addition of hydrogen bromide to the α,β-unsaturated system of 3-phenyl-2-propenoic acid

1983 ◽  
Vol 48 (10) ◽  
pp. 2952-2964 ◽  
Author(s):  
Otakar Červinka ◽  
Otomar Kříž
Keyword(s):  
Hydrogen Bromide ◽  
Uv Spectroscopy ◽  
Rate Determining Step ◽  
Propenoic Acid ◽  
Unsaturated System

Rate of addition of hydrogen bromide to meta- and para-substituted 3-phenyl-2-propenoic acids I was followed by polarography and UV spectroscopy. Rate of protonation either is the overall rate determining step or is at least comparable with the rate of the subsequent nucleophile attack.

Some Aspects of the Electroreduction of Niazid to Nicotinamide on Mercury Electrodes in Acidic Media

1992 ◽  
Vol 57 (9) ◽  
pp. 1836-1842 ◽  
Author(s):  
Rafael Marín Galvín ◽  
José Miguel Rodríguez Mellado
Keyword(s):  
Electron Transfer ◽  
Essential Role ◽  
Uv Spectroscopy ◽  
Acidic Media ◽  
Polarographic Wave ◽  
Rate Determining Step ◽  
Tafel Slopes ◽  
Reaction Orders ◽  
Mercury Electrodes ◽  
The Waves

The electroreduction of niazid on mercury electrodes has been studied in acidic media (pH < 6). Tafel slopes and reaction orders were obtained at potentials corresponding to the foot of the first polarographic wave. On the basis of both polarographic and voltammetric results it has been shown that the waves appearing at more negative potentials correspond to the reduction of nicotinamide. Protonation of niazid plays an essential role in its reduction and pK values of 1.4, 3.2 and 11.5 were obtained by UV spectroscopy. The process corresponding to the first wave is irreversible, being the second one-electron transfer the rate determining step. Above pH 4 the process is complex due to the overlapping of the waves caused by the occurrence of protonation reactions.

Studies of the variations in bond dissociation energies of aromatic compounds. I. Mono-bromo-aryles

1953 ◽  
Vol 219 (1138) ◽  
pp. 341-352 ◽  
Keyword(s):  
Hydrogen Bromide ◽  
Heat Of Formation ◽  
Activation Energies ◽  
Bond Dissociation Energies ◽  
First Order ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Rate Determining Step ◽  
First Order Kinetics ◽  
Aromatic Radicals

Investigation of the pyrolyses of bromobenzene, β -bromonaphthalene, α -bromonaphthalene, 9-bromophenanthrene and 9-bromoanthraeene in the presence of an excess of toluene has shown that reaction (1) Ar .Br → Ar • + Br (1) is the primary and rate-determining step of the pyrolysis. The progress of reaction was measured by the rate of formation of hydrogen bromide, and it was shown that this rate obeys first-order kinetics. The following values were obtained for the activation energies and frequency factors of unimolecular decompositions represented by equation (1): compound E (kcal/mole) 10 -13 v (sec -1 ) bromobenzene 70.9 2 β -bromonaphthalene 700 1.5 α -bromonaphthalene 70.9 3.5 9-bromophenanthrene 67.7 1 9-bromoanthracene 65.6 1.5 Assuming that recombination of bromine atoms with aromatic radicals does not involve any activation energy we conclude tha t the determined activation energies correspond to the respective C—Br bond dissociation energies. The effect of molecular structure on the C—Br bond dissociation energy is discussed. The heat of formation of the phenyl radical is determined, and this result is used for calculating the various Ph — X bond dissociation energies.

Pt-Pd Nanoalloy for the Unprecedented Activation of Carbon-Fluorine Bond at Low Temperature

2019 ◽  
Author(s):  
Raghu Nath Dhital ◽  
keigo nomura ◽  
Yoshinori Sato ◽  
Setsiri Haesuwannakij ◽  
Masahiro Ehara ◽  
...  
Keyword(s):  
Activation Energy ◽  
Low Temperature ◽  
Dft Calculations ◽  
Bond Activation ◽  
Mild Conditions ◽  
Selective Transformation ◽  
Rate Determining Step ◽  
Highly Active ◽  
Harsh Conditions ◽  
Reaction Profile

Carbon-Fluorine (C-F) bonds are considered the most inert organic functionality and their selective transformation under mild conditions remains challenging. Herein, we report a highly active Pt-Pd nanoalloy as a robust catalyst for the transformation of C-F bonds into C-H bonds at low temperature, a reaction that often required harsh conditions. The alloying of Pt with Pd is crucial to activate C-F bond. The reaction profile kinetics revealed that the major source of hydrogen in the defluorinated product is the alcoholic proton of 2-propanol, and the rate-determining step is the reduction of the metal upon transfer of the <i>beta</i>-H from 2-propanol. DFT calculations elucidated that the key step is the selective oxidative addition of the O-H bond of 2-propanol to a Pd center prior to C-F bond activation at a Pt site, which crucially reduces the activation energy of the C-F bond. Therefore, both Pt and Pd work independently but synergistically to promote the overall reaction

Electron Donation by Low-Crystalline Ba-La-Ce Oxygen-Deficient Composite Oxide Accumulating on Ru Nanoparticles for Ammonia Synthesis under Mild Conditions

2019 ◽  
Author(s):  
Katsutoshi Sato ◽  
Shin-ichiro Miyahara ◽  
Yuta Ogura ◽  
Kotoko Tsujimaru ◽  
Yuichiro Wada ◽  
...  
Keyword(s):  
Ammonia Synthesis ◽  
Bond Cleavage ◽  
Synthesis Process ◽  
Strong Electron ◽  
Mild Conditions ◽  
Ru Nanoparticles ◽  
Rate Determining Step ◽  
Highly Active ◽  
Composite Oxides ◽  
Low Crystalline

<p>To mitigate global problems related to energy and global warming, it is helpful to develop an ammonia synthesis process using catalysts that are highly active under mild conditions. Here we show that the ammonia synthesis activity of Ru/Ba/LaCeO<i><sub>x</sub></i> pre-reduced at 700 °C is the highest reported among oxide-supported Ru catalysts. Our results indicate that low crystalline oxygen-deficient composite oxides, which include Ba<sup>2+</sup>, Ce<sup>3+</sup> and La<sup>3+</sup>, with strong electron-donating ability, accumulate on Ru particles and thus promote N≡N bond cleavage, which is the rate determining step for ammonia synthesis.</p>

Electron Donation by Low-Crystalline Ba-La-Ce Oxygen-Deficient Composite Oxide Accumulating on Ru Nanoparticles for Ammonia Synthesis under Mild Conditions

2019 ◽  
Author(s):  
Katsutoshi Sato ◽  
Shin-ichiro Miyahara ◽  
Yuta Ogura ◽  
Kotoko Tsujimaru ◽  
Yuichiro Wada ◽  
...  
Keyword(s):  
Ammonia Synthesis ◽  
Bond Cleavage ◽  
Synthesis Process ◽  
Strong Electron ◽  
Mild Conditions ◽  
Ru Nanoparticles ◽  
Rate Determining Step ◽  
Highly Active ◽  
Composite Oxides ◽  
Low Crystalline

<p>To mitigate global problems related to energy and global warming, it is helpful to develop an ammonia synthesis process using catalysts that are highly active under mild conditions. Here we show that the ammonia synthesis activity of Ru/Ba/LaCeO<i><sub>x</sub></i> pre-reduced at 700 °C is the highest reported among oxide-supported Ru catalysts. Our results indicate that low crystalline oxygen-deficient composite oxides, which include Ba<sup>2+</sup>, Ce<sup>3+</sup> and La<sup>3+</sup>, with strong electron-donating ability, accumulate on Ru particles and thus promote N≡N bond cleavage, which is the rate determining step for ammonia synthesis.</p>

Mechanistic Insights into Fe Catalyzed α-C-H Oxidations of Tertiary Amines

2019 ◽  
Author(s):  
Christopher J. Legacy ◽  
Frederick T. Greenaway ◽  
Marion Emmert
Keyword(s):  
Free Radical ◽  
Catalytic Mechanism ◽  
Catalyst System ◽  
Oxidation Products ◽  
Tertiary Amines ◽  
Catalyst Activation ◽  
Rate Determining Step ◽  
Fe Catalyst ◽  
Ligand Coordination ◽  
Rate Kinetics

We report detailed mechanistic investigations of an iron-based catalyst system, which allows the α-C-H oxidation of a wide variety of amines, including acyclic tertiary aliphatic amines, to afford dealkylated or amide products. In contrast to other catalysts that affect α-C-H oxidations of tertiary amines, the system under investigation employs exclusively peroxy esters as oxidants. More common oxidants (e.g. tBuOOH) previously reported to affect amine oxidations via free radical pathways do not provide amine α-C-H oxidation products in combination with the herein described catalyst system. Motivated by this difference in reactivity to more common free radical systems, the investigations described herein employ initial rate kinetics, kinetic profiling, Eyring studies, kinetic isotope effect studies, Hammett studies, ligand coordination studies, and EPR studies to shed light on the Fe catalyst system. The obtained data suggest that the catalytic mechanism proceeds through C-H abstraction at a coordinated substrate molecule. This rate-determining step occurs either at an Fe(IV) oxo pathway or a 2-electron pathway at a Fe(II) intermediate with bound oxidant. We further show via kinetic profiling and EPR studies that catalyst activation follows a radical pathway, which is initiated by hydrolysis of PhCO3 tBu to tBuOOH in the reaction mixture. Overall, the obtained mechanistic data support a non-classical, Fe catalyzed pathway that requires substrate binding, thus inducing selectivity for α-C-H functionalization.<br>

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