Generation and properties of 4,9- and 3,8-methano[11]annulenylidenes

Jones, W. M.; Labar, Russell A.; Brinker, Udo H.; Gebert, P

doi:10.1021/ja00461a034

Cited by 41 publications

(19 citation statements)

References 13 publications

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“…According to the molecular orbital theory [39][40][41][42][43], chemical stability of all modified starch molecules is very high because the energy values of corresponding HOMO and LUMO are negative. Moreover, the difference in stability is easily understood in terms of the HOMO (Lewis base)-LUMO (Lewis acid) interaction; namely, a smaller HOMO-LUMO gap (Δ ) helps in more electrotransition in general, so it is unfavorable for the formation of a Lewis steady molecule.…”

Section: Chemical Stability Of Three Types Of Oxidized Starch-based Amentioning

confidence: 99%

Theoretical Insights into Three Types of Oxidized Starch-Based Adhesives: Chemical Stability, Water Resistance, and Shearing Viscosity from a Molecular Viewpoint

Junxi

Zhao

et al. 2016

Journal of Chemistry

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To better understand the origin and difference associated with chemical stability, water resistance, and shearing viscosity of three types of different oxidized modified starch-based adhesives, a detailed theoretical investigation from a molecular viewpoint has been performed using the AM1 semiempirical level and the DFT-B3LYP level, respectively. As a result, our findings suggest that, by Mulliken population analysis (MPA), frontier orbital analysis, and electrostatic potential (EP) analysis based on B3LYP/6-31G calculations, the chemical stability, water resistance, and shearing viscosity of the oxidized modified starch-based adhesives are uniformly improved and corresponding difference for each property presents an identical order: the oxidized grafted cross-linked starch-based adhesive > the oxidized grafted starch-based adhesive > the oxidized starch-based adhesive, which is well consistent with experimental results.

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Section: Chemical Stability Of Three Types Of Oxidized Starch-based Amentioning

confidence: 99%

Theoretical Insights into Three Types of Oxidized Starch-Based Adhesives: Chemical Stability, Water Resistance, and Shearing Viscosity from a Molecular Viewpoint

Junxi

Zhao

et al. 2016

Journal of Chemistry

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“…Note that, as pictured on the PES in Figure 2, the step of electron transfer (IM2-1 → IM3-1) is a completely endoergic process. This can be perfectly explained by the differential orbital energies, , [41][42][43][44] proposing that the smaller differential orbital energy corresponds to the easier reaction. As listed in Table 2, the difference decreases as the order of > > .…”

mentioning

confidence: 87%

CCl₄Activation Mechanisms by Gas-Phase CHBr^•^–and CBr₂^•^–: A Comparative Study

Junxi¹,

Wang²,

Hasi³

et al. 2013

Bulletin of the Korean Chemical Society

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The mechanisms concerning C-Cl activation of CCl4 by CHBr•-and CBr2•-have been comparatively investigated in theory. Optimized geometries and frequencies of all stationary points on PES are obtained at the BhandHLYP/aug-cc-pVTZ level of theory, and then the energy profiles are refined at the QCISD(T) method with the aug-cc-pVTZ basis by using the BhandHLYP/aug-cc-pVTZ optimized geometries. Our calculated findings suggest that in the title reactions the major mechanisms consist of both Cl-abstraction and SN2 substitution reactions. Also, a succeeding pathway described by electron transfer was revealed before the initial Cl-abstraction products separate. Those are consistent with relevant experimental results.

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“…Moreover, the difference in stability of these adducts is easily understood in terms of the HOMO (Lewis base; i.e., CHX ·− /CX ·− 2 )-LUMO (Lewis acid; i.e., CHCl 3 ) interaction. According to the perturbation theory, [21][22][23][24][25] both a smaller HOMO-LUMO gap and a larger overlap between them results in a greater Lewis adduct stabilization. According to our theoretical investigations, we note that the energy of the HOMO decreases in the order (kJ mol −1 ) CHCl ·− (−136.53) > CHBr ·− (−162.78) > CHI ·− (−170.71) and CCl ·− 2 (−254.67) > CBr ·− 2 (−267.80) > CI ·− 2 (−286.24).…”

Section: Reamentioning

confidence: 99%

Theoretical study of the reactivity trends in the Cl-abstraction reactions of CHCl3 + CHX· − /CX2 · − (X = Cl, Br and I)

2011

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To better understand how and to what extent the halosubstituted carbene radical anions effect the chlorine abstraction of CHCl 3 , a detailed theoretical investigation has been performed at the UMP2/6-311++G (d, p)/RECP level of theory. The model system CHCl 3 + CHX ·− /CX ·− 2 (X = Cl, Br, and I) has been chosen for the present study. According to the detailed discussions of geometries and energetics of the optimized stationary points, our theoretical findings suggest that the Cl-abstraction reactions by CHX ·− are energetically favourable, indicating the less massive substitution X in CHX ·− the easier abstraction reaction, as compared to those by CX ·− 2 , which are energetically unfavourable and would be endothermic.

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Generation and properties of 4,9- and 3,8-methano[11]annulenylidenes

Cited by 41 publications

References 13 publications

Theoretical Insights into Three Types of Oxidized Starch-Based Adhesives: Chemical Stability, Water Resistance, and Shearing Viscosity from a Molecular Viewpoint

Theoretical Insights into Three Types of Oxidized Starch-Based Adhesives: Chemical Stability, Water Resistance, and Shearing Viscosity from a Molecular Viewpoint

CCl₄Activation Mechanisms by Gas-Phase CHBr^•^–and CBr₂^•^–: A Comparative Study

Theoretical study of the reactivity trends in the Cl-abstraction reactions of CHCl3 + CHX· − /CX2 · − (X = Cl, Br and I)

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Generation and properties of 4,9- and 3,8-methano[11]annulenylidenes

Cited by 41 publications

References 13 publications

Theoretical Insights into Three Types of Oxidized Starch-Based Adhesives: Chemical Stability, Water Resistance, and Shearing Viscosity from a Molecular Viewpoint

Theoretical Insights into Three Types of Oxidized Starch-Based Adhesives: Chemical Stability, Water Resistance, and Shearing Viscosity from a Molecular Viewpoint

CCl4Activation Mechanisms by Gas-Phase CHBr•–and CBr2•–: A Comparative Study

Theoretical study of the reactivity trends in the Cl-abstraction reactions of CHCl3 + CHX· − /CX2 · − (X = Cl, Br and I)

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CCl₄Activation Mechanisms by Gas-Phase CHBr^•^–and CBr₂^•^–: A Comparative Study