Aluminum(i) β-diketiminato complexes activate C(sp2)–F and C(sp3)–F bonds by different oxidative addition mechanisms: a DFT study

DFT computations reveal different reaction mechanisms for the oxidative addition of C(sp2)–F and C(sp3)–F bonds to the Al(i) complexes: a concerted mechanism for C(sp2)–F and a stepwise mechanism for C(sp3)–F involving fluoride transfer and the formation and recombination of an ion pair.

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Tropospheric degradation of 2-fluoropropene (CH3CF CH2) initiated by hydroxyl radical: Reaction mechanisms, kinetics and atmospheric implications from DFT study

Chemosphere ◽

10.1016/j.chemosphere.2019.124556 ◽

2020 ◽

Vol 238 ◽

pp. 124556 ◽

Cited By ~ 5

Author(s):

Nand Kishor Gour ◽

Kaushik Borthakur ◽

Subrata Paul ◽

Ramesh Chandra Deka

Keyword(s):

Hydroxyl Radical ◽

Reaction Mechanisms ◽

Radical Reaction ◽

Dft Study

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Reaction mechanism studies. 5. The mechanism of the diaxial → diequatorial rearrangement of β-chlorothioethers

Canadian Journal of Chemistry ◽

10.1139/v68-002 ◽

1968 ◽

Vol 46 (1) ◽

pp. 9-13 ◽

Cited By ~ 5

Author(s):

J. F. King ◽

K. Abikar

Keyword(s):

Reaction Mechanism ◽

Transition State ◽

Nitro Group ◽

Ion Pair ◽

Concerted Mechanism

p-Methoxy- and p-nitro substituted analogues (1b and 1c) of the diaxial β-chlorothioether 2β-chloro-3α-(phenylthio)-5α-cholestane (1a), have been prepared and found to undergo the diaxial → diequatorial rearrangement. The rates of rearrangement of these compounds show the sequence p-methoxy > H > p-nitro. It is concluded that the transition state for the rearrangement is polarized in the sense of a sulfonium chloride (3). The rearrangement of 1a is 1600 times faster in butanol than in decalin (at 110°). There is thus no inherent insensitivity to solvent change in a rearrangement in which there may be a "four-atom arrangement" in the transition state, a conclusion relevant to previous work on the diaxial → diequatorial rearrangement of 1,2-dibromides (1). It was further found that the nitro group slowed the rearrangement (at 110°) more in butanol than in decalin, an observation regarded as consistent with, but not requiring, the incursion of a merged ion-pair, cyclic concerted mechanism.

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DFT study on the reaction mechanisms behind the catalytic oxidation of benzyl alcohol into benzaldehyde by O2 over anatase TiO2 surfaces with hydroxyl groups: Role of visible-light irradiation

Applied Catalysis B Environmental ◽

10.1016/j.apcatb.2015.01.035 ◽

2015 ◽

Vol 170-171 ◽

pp. 135-143 ◽

Cited By ~ 35

Author(s):

Hisayoshi Kobayashi ◽

Shinya Higashimoto

Keyword(s):

Visible Light ◽

Benzyl Alcohol ◽

Catalytic Oxidation ◽

Visible Light Irradiation ◽

Reaction Mechanisms ◽

Anatase Tio2 ◽

Light Irradiation ◽

Dft Study ◽

Hydroxyl Groups

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Reaction mechanisms of DNT with hydroxyl radicals for advanced oxidation processes—a DFT study

Journal of Molecular Modeling ◽

10.1007/s00894-017-3277-0 ◽

2017 ◽

Vol 23 (4) ◽

Cited By ~ 3

Author(s):

Yang Zhou ◽

Zhilin Yang ◽

Hong Yang ◽

Chaoyang Zhang ◽

Xiaoqiang Liu

Keyword(s):

Hydroxyl Radicals ◽

Reaction Mechanisms ◽

Advanced Oxidation Processes ◽

Advanced Oxidation ◽

Dft Study ◽

Oxidation Processes

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Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Brønsted acids. NMR and DFT study of these cations and their reactions

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.14.268 ◽

2018 ◽

Vol 14 ◽

pp. 2897-2906 ◽

Cited By ~ 3

Author(s):

Stanislav V Lozovskiy ◽

Alexander Yu Ivanov ◽

Olesya V Khoroshilova ◽

Aleksander V Vasilyev

Keyword(s):

Dft Calculations ◽

Reaction Mechanisms ◽

Dft Study ◽

Bronsted Acids ◽

Allyl Alcohols ◽

High Yields ◽

Hydrolysis Of

In strong Brønsted acids (CF3SO3H, FSO3H, D2SO4), (arysulfonyl)allenes (ArSO2–CR1=C=CR2R3) and (arylsulfinyl)allenes (ArSO–CR1=C=CR2R3) undergo cyclization into the corresponding stable 1,2-oxathiolium ions, which were studied by means of NMR and DFT calculations. Quenching of solutions of these cations with low nucleophilic media, aqueous HCl, leads to their deprotonation with a stereoselective formation of (arysulfonyl)butadienes (for instance, ArSO2–CR1=C–C(Me)=CH2, for R2 = R3 = Me, yields of 87–98%). Reactions of (arysulfonyl)allenes in the system TfOH (0.1 equiv)–HFIP (hexafluoropropan-2-ol) followed by hydrolysis give rise to allyl alcohols (ArSO2–CR1=CH–C(OH)R2R3, yields of 78–99%). Reflux of solutions of (arysulfonyl)allenes in the presence of TfOH (1 equiv) in 1,2-dichlorobenzene leads to the cyclization into thiochromene 1,1-dioxides in high yields. Under the action of TfOH or AlX3 (X = Cl, Br) followed by hydrolysis of reaction mixtures, (arylsulfinyl)allenes give allyl alcohols (ArSO2–CR1=CH–C(OH)R2R3). Plausible reaction mechanisms have been proposed for all studied reactions.

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Oxidative addition transition states of Pd(0) complexes in polar solvent—a DFT study involving implicit and explicit solvation

Tetrahedron ◽

10.1016/j.tet.2013.03.095 ◽

2013 ◽

Vol 69 (27-28) ◽

pp. 5715-5718 ◽

Cited By ~ 29

Author(s):

Eirik Lyngvi ◽

Franziska Schoenebeck

Keyword(s):

Polar Solvent ◽

Transition States ◽

Oxidative Addition ◽

Dft Study ◽

Implicit And Explicit ◽

Explicit Solvation

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Hydration and ion pair formation in common aqueous La(iii) salt solutions – a Raman scattering and DFT study

Dalton Transactions ◽

10.1039/c4dt03003f ◽

2015 ◽

Vol 44 (1) ◽

pp. 295-305 ◽

Cited By ~ 28

Author(s):

Wolfram W. Rudolph ◽

Gert Irmer

Keyword(s):

Raman Spectrum ◽

Raman Scattering ◽

Ion Pair ◽

Pair Formation ◽

Dft Study ◽

Salt Solutions ◽

Left Hand ◽

Ion Pair Formation ◽

Right Hand

Left hand side: Raman spectrum of a 0.622 mol L−1La(ClO4)3(aq). Weak, polarized band at 343 cm−1assigned to symmetric La–O stretch of [La(OH2)9]3+. Bands at 463 and 630 cm−1due to ClO4−(aq). The inset shows the isotropic band in more detail. Right hand side: Structure of [La(OH2)9]3+(symmetryD3).

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