scholarly journals Tetrel Bond between 6-OTX3-Fulvene and NH3: Substituents and Aromaticity

Molecules ◽  
2018 ◽  
Vol 24 (1) ◽  
pp. 10 ◽  
Author(s):  
Ming-Chang Hou ◽  
Shu-Bin Yang ◽  
Qing-Zhong Li ◽  
Jian-Bo Cheng ◽  
Hai-Bei Li ◽  
...  

Carbon bonding is a weak interaction, particularly when a neutral molecule acts as an electron donor. Thus, there is an interesting question of how to enhance carbon bonding. In this paper, we found that the –OCH3 group at the exocyclic carbon of fulvene can form a moderate carbon bond with NH3 with an interaction energy of about −10 kJ/mol. The –OSiH3 group engages in a stronger tetrel bond than does the –OGeH3 group, while a reverse result is found for both –OSiF3 and –OGeF3 groups. The abnormal order in the former is mainly due to the stronger orbital interaction in the –OSiH3 complex, which has a larger deformation energy. The cyano groups adjoined to the fulvene ring not only cause a change in the interaction type, from vdW interactions in the unsubstituted system of –OCF3 to carbon bonding, but also greatly strengthen tetrel bonding. The formation of tetrel bonding has an enhancing effect on the aromaticity of the fulvene ring.

Molecules ◽  
2019 ◽  
Vol 24 (18) ◽  
pp. 3370 ◽  
Author(s):  
Tiddo J. Mooibroek

A systematic evaluation of the CSD and the PDB in conjunction with DFT calculations reveal that non-covalent Carbon-bonding interactions with X–CH3 can be weakly directional in the solid state (P ≤ 1.5) when X = N or O. This is comparable to very weak CH hydrogen bonding interactions and is in line with the weak interaction energies calculated (≤ –1.5 kcal·mol−1) of typical charge neutral adducts such as [Me3N-CH3···OH2] (2a). The interaction energy is enhanced to ≤–5 kcal·mol−1 when X is more electron withdrawing such as in [O2N-CH3··O=Cdme] (20b) and to ≤18 kcal·mol−1 in cationic species like [Me3O+-CH3···OH2]+ (8a).


2001 ◽  
Vol 19 (3) ◽  
pp. 237-244 ◽  
Author(s):  
Nikolai V. Nikolenko

The energies of unoccupied and occupied orbitals were used as the correlation parameters between the electronic and adsorptive properties of organic molecules. A model describing the chemisorption of organic compounds on CaCO3 involving two types of interaction, i.e. two-electron, donor–acceptor interaction HOMO(adsorbent) → LUMO(adsorbate) and four-electron, three-orbital interaction HOMO(adsorbent) → {LUMO(adsorbate) + HOMO(adsorbate)}, was proposed. It was concluded that strengthening of the bond involved in chemisorption occurred if the energies of the occupied orbitals associated with the adsorbate and adsorbent were concurrent.


Molecules ◽  
2018 ◽  
Vol 23 (10) ◽  
pp. 2642 ◽  
Author(s):  
Mehdi Esrafili ◽  
Parisasadat Mousavian

In recent years, noncovalent interactions involving group-14 elements of the periodic table acting as a Lewis acid center (or tetrel-bonding interactions) have attracted considerable attention due to their potential applications in supramolecular chemistry, material science and so on. The aim of the present study is to characterize the geometry, strength and bonding properties of strong tetrel-bond interactions in some charge-assisted tetrel-bonded complexes. Ab initio calculations are performed, and the results are supported by the quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) approaches. The interaction energies of the anionic tetrel-bonded complexes formed between XF3M molecule (X=F, CN; M=Si, Ge and Sn) and A− anions (A−=F−, Cl−, Br−, CN−, NC− and N3−) vary between −16.35 and −96.30 kcal/mol. The M atom in these complexes is generally characterized by pentavalency, i.e., is hypervalent. Moreover, the QTAIM analysis confirms that the anionic tetrel-bonding interaction in these systems could be classified as a strong interaction with some covalent character. On the other hand, it is found that the tetrel-bond interactions in cationic tetrel-bonded [p-NH3(C6H4)MH3]+···Z and [p-NH3(C6F4)MH3]+···Z complexes (M=Si, Ge, Sn and Z=NH3, NH2CH3, NH2OH and NH2NH2) are characterized by a strong orbital interaction between the filled lone-pair orbital of the Lewis base and empty BD*M-C orbital of the Lewis base. The substitution of the F atoms in the benzene ring provides a strong orbital interaction, and hence improved tetrel-bond interaction. For all charge-assisted tetrel-bonded complexes, it is seen that the formation of tetrel-bond interaction is accompanied bysignificant electron density redistribution over the interacting subunits. Finally, we provide some experimental evidence for the existence of such charge-assisted tetrel-bond interactions in crystalline phase.


Molecules ◽  
2021 ◽  
Vol 26 (15) ◽  
pp. 4558
Author(s):  
Le Lu ◽  
Ruimao Hua

The dual XH (OH and CH) hydrogen-bond-donating property of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and the strong dual XH–π interaction with arenes were firstly disclosed by theoretical studies. Here, the high accuracy post-Hartree–Fock methods, CCSD(T)/CBS, reveal the interaction energy of HFIP/benzene complex (−7.22 kcal/mol) and the contribution of the electronic correlation energy in the total interaction energy. Strong orbital interaction between HFIP and benzene was found by using the DFT method in this work to disclose the dual XH–π intermolecular orbital interaction of HFIP with benzene-forming bonding and antibonding orbitals resulting from the orbital symmetry of HFIP. The density of states and charge decomposition analyses were used to investigate the orbital interactions. Isopropanol (IP), an analogue of HFIP, and chloroform (CHCl3) were studied to compare them with the classical OH–π, and non-classical CH–π interactions. In addition, the influence of the aggregating effect of HFIP, and the numbers of substituted methyl groups in benzene rings were also studied. The interaction energies of HFIP with the selected 24 common organic compounds were calculated to understand the role of HFIP as solvent or additive in organic transformation in a more detailed manner. A single-crystal X-ray diffraction study of hexafluoroisopropyl benzoate further disclosed and confirmed that the CH of HFIP shows the non-classical hydrogen-bond-donating behavior.


2018 ◽  
pp. 26-30

Coulomb and even-odd effects in cold and super-asymmetric fragmentation for thermal neutron induced fission of 235U M. Montoya Instituto Peruano de Energía Nuclear, Canadá 1470, San Borja, Lima, Peru Universidad Nacional de Ingeniería, Av. Túpac Amaru 210, Rímac, Lima, Peru DOI: https://doi.org/10.33017/RevECIPeru2015.0004/ Abstract The Coulomb effects hypothesis is used to interpret even-odd effects of maximum total kinetic energy as a function of mass and charge of fragments from thermal neutron induced fission of 235U. Assuming spherical fragments at scission, the Coulomb interaction energy between fragments ( ) is higher than the -value, the available energy. Therefore at scission the fragments must be deformed, so that the Coulomb interaction energy does not exceed the -value. The fact that the even-odd effects in the maximum total kinetic energy as a function of the charge and mass, respectively, are lower than the even-odd effects of  is consistent with the assumption that odd mass fragments are softer than the even-even fragments. Even-odd effects of charge distribution in super asymmetric fragmentation also are interpreted with the Coulomb effect hypothesis. Because the difference between  and   increases with asymmetry, fragmentations require higher total deformation energy to occur. Higher deformation energy of the fragments implies lower free energy to break pairs of nucleons. This explains why in the asymmetric fragmentation region, the even-odd effects of the distribution of proton number and neutron number increases with asymmetry. Based on a similar reasoning, a prediction of a relatively high even-odd effect in symmetric fragmentations is proposed. Keywords: cold fission, asymmetric fragmentation, symmetric fission, kinetic energy, uranium 235 Resumen  La hipótesis del efecto Coulomb es usado para interpretar los efectos par-impar sobre la energía total máxima en función de la masa y carga de los fragmentos de la fisión inducida por neutrones térmicos del 235U. Suponiendo que en la escisión los fragmentos son esféricos, la energía de interacción coulombiana entre fragmentos ( ) es mayor que el valor , la energía disponible. Entonces, los fragmentos en la escisión deben estar deformados, de modo que la energía de interacción coulombiana no exceda el valor  de la reacción. El hecho de que los efectos par-impar sobre el valor máximo de la energía cinética total en función de la carga y la masa, respectivamente, son menores que los efectos par-impar de  es consistente con la suposición que los fragmentos con masa impar son más blandos que los fragmentos par-par. Los efectos par-impar de la distribución de carga en las fragmentaciones super asimétricas también son interpretados con la hipótesis del efecto Coulomb. Debido a que la diferencia entre  y   crece con la asimetría, las fragmentaciones requieren mayor energía total de deformación para ocurrir. Mayor energía de deformación de los fragmentos implica menor energía libre para romper pares de nucleones. Esto explica por qué en la region de asimetría, los efectos par-impar en la distribución de número de protons y número de neutrones crece con la asimetría. Basado en un razonamiento similar, se predice un alto efecto par-impar en las fragmentaciones simétricas. Descriptores: fisión fría, fragmentación asimétrica, fisión simétrica, energía cinética, uranio 235.


1982 ◽  
Vol 35 (8) ◽  
pp. 1513 ◽  
Author(s):  
PE Schipper

The fully expanded expression for the Boltzmann-averaged pairwise intermolecular interaction energy of two molecules B and C of arbitrary symmetry is determined in the weak interaction limit (<kT), including all electrostatic, induction and dispersion interactions having an r-n dependence (where r is the B-C separation) for which n < 11. The method exploits the 'point moment function' (PMF) approach in which the Boltzmann-averaged energy is shown to reduce to a sum of terms, each containing a product of a PMF on B, and one on C. The point moment functions may be obtained in a general analytic form by averaging an arbitrary multipolar product for the isolated molecule. Two types of PMF (Δ, point chirality function, and Λ, point achirality function) are identified, leading to a natural division of contributions to the intermolecular interaction energy into those that are insensitive (ΛΛ contributions) and sensitive (ΔΔ contributions) to molecular chirality.


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