Gas-phase acidity, bond dissociation energy and enthalpy of formation of fluorine-substituted benzenes: A theoretical study

Namazian, Mansoor; Coote, Michelle L.

doi:10.1016/j.jfluchem.2009.04.003

Cited by 20 publications

(7 citation statements)

References 20 publications

(32 reference statements)

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“…It is well known that the CH acidity of benzene is rather weak with Gibbs free energy measured experimentally 391 kcal/mol . Theoretical estimation of heterolytic bond dissociation enthalpy in benzene is equal to 400.5 kcal/mol at the CBS‐QB3 level and also our B3LYP/6‐311++G(d,p) calculations give the same number. This value can be however significantly lowered by proper substitution .…”

Section: Resultssupporting

confidence: 75%

“…Theoretical estimation of heterolytic bond dissociation enthalpy in benzene is equal to 400.5 kcal/mol at the CBS‐QB3 level and also our B3LYP/6‐311++G(d,p) calculations give the same number. This value can be however significantly lowered by proper substitution . On the other hand our estimation of the enthalpy of CH bond of pentafulvene is 388.6 kcal/mol for the heterolytic cleavage of the CH bond in exo‐position and 397.6/398.4 kcal/mol for 2‐position and 3‐position in the ring, respectively.…”

Section: Resultssupporting

confidence: 65%

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Comparative studies on CH⋯F⁻hydrogen bond formation in benzene and exocyclically substituted pentafulvene derivatives

Ozimiński

Krygowski

2013

J. Phys. Org. Chem.

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Optimization of CH⋯F À complexes of exo-substituted pentafulvene and meta-substituted and para-substituted benzene (substituents: NMe 2 , NHMe, NH 2 , NHOH, OH, OMe, Br, Cl, F, Me, CCH, CF 3 , CONH 2 , COMe, CHO, NO 2 , NO, and CN) have been performed at the density functional theory level by using Becke hybrid B3LYP functional with 6-311++G(d,p) basis set. The acidity of the ring CH bond in benzene and fulvene are of similar magnitude, whereas the acidity of the fulvene exocyclic CH 2 group is significantly higher. Various properties based on the H⋯F À hydrogen bond (bond length, electron density at BCP, and bond dissociation energy), and the whole molecule (HOMA, sEDA, pEDA, substituent active region, and substituent effect stabilization energy) were analyzed and compared between the fulvene and benzene systems. Sensitivity of the ring CH⋯F À hydrogen bond and other substituent dependent properties to substituent effect is substantially greater in fulvene than that of benzene derivatives. In fulvene, the 3-position is more sensitive than the 4-position. The sEDA and pEDA parameters used to measure sigma-electron and pi-electron excess/deficiency of the ring are mutually correlated for the studied systems.

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Section: Resultssupporting

confidence: 75%

Section: Resultssupporting

confidence: 65%

Comparative studies on CH⋯F⁻hydrogen bond formation in benzene and exocyclically substituted pentafulvene derivatives

Ozimiński

Krygowski

2013

J. Phys. Org. Chem.

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“…The pioneering research of Kirkbride and Davidson [5] in this direction was followed for half a century by studies that produced many important findings [6][7][8][9].…”

Section: Introductionmentioning

confidence: 99%

Comparison of theoretical methods for assessing the heat of formation of C1 and C2 chlorofluorocarbons and hydrochlorofluorocarbons

Zhang

Zhou

et al. 2010

Journal of Fluorine Chemistry

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“…This observation is in clear contrast to the photoinduced Pd-catalyzed Heck reaction of alkyl bromides with styrenes recently reported by the Fu group 28 , which proposed β-hydride elimination as the product forming step, and where the electronic nature of the styrene substrate was insignificant. Possible HAT reactions from the pentafluorobenzene, which may intervene in the productive reaction pathway, were also ruled out by comparing the bond dissociation energies (BDEs) of the related C–H bonds 22 , 56 and DFT computations of the HAT barrier (Supplementary Fig. 18 ).…”

Section: Resultsmentioning

confidence: 99%

Direct C(sp2)–H alkylation of unactivated arenes enabled by photoinduced Pd catalysis

et al. 2020

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Despite the fundamental importance of efficient and selective synthesis of widely useful alkylarenes, the direct catalytic C(sp2)–H alkylation of unactivated arenes with a readily available alkyl halide remains elusive. Here, we report the catalytic C(sp2)–H alkylation reactions of unactivated arenes with alkyl bromides via visible-light induced Pd catalysis. The reaction proceeds smoothly under mild conditions without any skeletal rearrangement of the alkyl groups. The direct syntheses of structurally diverse linear and branched alkylarenes, including the late-stage phenylation of biologically active molecules and an orthogonal one-pot sequential Pd-catalyzed C–C bond-forming reaction, are achieved with exclusive chemoselectivity and exceptional functional group tolerance. Comprehensive mechanistic investigations through a combination of experimental and computational methods reveal a distinguishable Pd(0)/Pd(I) redox catalytic cycle and the origin of the counter-intuitive reactivity differences among alkyl halides.

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Gas-phase acidity, bond dissociation energy and enthalpy of formation of fluorine-substituted benzenes: A theoretical study

Cited by 20 publications

References 20 publications

Comparative studies on CH⋯F⁻hydrogen bond formation in benzene and exocyclically substituted pentafulvene derivatives

Comparative studies on CH⋯F⁻hydrogen bond formation in benzene and exocyclically substituted pentafulvene derivatives

Comparison of theoretical methods for assessing the heat of formation of C1 and C2 chlorofluorocarbons and hydrochlorofluorocarbons

Direct C(sp2)–H alkylation of unactivated arenes enabled by photoinduced Pd catalysis

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Gas-phase acidity, bond dissociation energy and enthalpy of formation of fluorine-substituted benzenes: A theoretical study

Cited by 20 publications

References 20 publications

Comparative studies on CH⋯F−hydrogen bond formation in benzene and exocyclically substituted pentafulvene derivatives

Comparative studies on CH⋯F−hydrogen bond formation in benzene and exocyclically substituted pentafulvene derivatives

Comparison of theoretical methods for assessing the heat of formation of C1 and C2 chlorofluorocarbons and hydrochlorofluorocarbons

Direct C(sp2)–H alkylation of unactivated arenes enabled by photoinduced Pd catalysis

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Comparative studies on CH⋯F⁻hydrogen bond formation in benzene and exocyclically substituted pentafulvene derivatives

Comparative studies on CH⋯F⁻hydrogen bond formation in benzene and exocyclically substituted pentafulvene derivatives