An MP2 and DFT study of heterocyclic hydrogen complexes CnHmYHX with n=2, m=4 or 5, Y=O, S or N and X=F or Cl

Oliveira, Boaz G.; Santos, Eva; Duarte, E.M.; Araújo, Regiane C. M. U.; Ramos, Mozart N.; Carvalho, Antônio B.

doi:10.1016/j.saa.2003.10.006

Cited by 27 publications

(11 citation statements)

References 14 publications

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“…The n lone electron pairs of sulfur atom may act as an electron donor, the hydrogen atoms of the CH 2 groups of the thiirane ring may act as an electron acceptor. Oliveira and co-workers [22][23][24][25][26][27] studied the hydrogen bonds formed by (CH 2 ) 2 S and similar heterorings with monoprotic acids and nucleophilic species.…”

Section: Introductionmentioning

confidence: 99%

A computational study on the nature of the halogen bond between sulfides and dihalogen molecules

Zhang

Zeng

et al. 2011

Struct Chem

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The characteristics and nature of the halogen bonding in a series of BÁÁÁXY (B = H 2 S, H 2 CS, (CH 2 ) 2 S; XY = ClF, Cl 2 , BrF, BrCl, Br 2 ) complexes were analyzed by means of the quantum theory of ''atoms in molecules'' (QTAIM) and ''natural bond orbital'' (NBO) methodology at the second-order Møller-Plesset (MP2) level. Electrostatic potential, bond length, interaction energy, topological properties of the electron density, the dipole moment, and the charge transfer were investigated systematically. For the same electron donor, the interaction energies follows the BÁÁÁBrF [ BÁÁÁClF [ BÁÁÁBrCl [ BÁÁÁBr 2 [ BÁÁÁCl 2 [ BÁÁÁClBr order. For the same electron acceptor, the interaction energies increase in the sequence of H 2 S, H 2 CS, and (CH 2 ) 2 S. Topological analyses show these halogen bonding interactions belong to weak interactions with an electrostatic nature. It was found that the strength of the halogen-bonding interaction correlates well with the electrostatic potential associated with halogen atom and the amount of charge transfer from sulfides to dihalogen molecules, indicating that electrostatic interaction plays an important role in these halogen bonds. Charge transfer is also an important factor in the halogen bonds involved with dihalogen molecules.Keywords Halogen bond Á Topological analysis of electron density Á Natural bond orbital analysis Á Electrostatic interaction Á Charge transfer

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Section: Introductionmentioning

confidence: 99%

A computational study on the nature of the halogen bond between sulfides and dihalogen molecules

Zhang

Zeng

et al. 2011

Struct Chem

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“…This phenomenon was observed some time ago by Pinchas [14] and Sandorfy [15]. By definition, the strengthening of proton donor bonds is found on blue-shifting hydrogen bonds because their stretch frequencies are shifted upwards [16][17][18][19][20][21][22]. Although it is very common to interpret blue-shifts in specific proton donor centers, such as for instance the C-H bond of fluoroform (HCF 3 ) [23], the present study admits the possibility of fluoroform forming intermolecular p complexes with ethylene (C 2 H 4 ), propylene (C 2 H 3 (CH 3 )) and t-butylene (C 2 H 2 (CH 3 ) 2 ).…”

Section: Introductionmentioning

confidence: 81%

Evidence for blue-shifting and red-shifting effects in the C2H4···HCF3, C2H3(CH3)···HCF3 and C2H2(CH3)2···HCF3 complexes: π and improper-π hydrogen bonds

Oliveira

Araújo

Ramos

2010

Journal of Molecular Structure: THEOCHEM

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“…In this context, it is important to remember that binary hydrogen complexes formed by aziridine and Lewis' acids are more stable than those whose proton acceptors are oxirane or thiirane [39][40][41]. In addition, it is worth noting that the formation of multiple hydrogen bonds leads ammonia to behave bilaterally as either a proton acceptor or donor, although our interest here is restricted to investigating if this condition truly affects stabilization of the hydrogen-bonded complex [42][43][44].…”

Section: Introductionmentioning

confidence: 99%

Theoretical aspects of binary and ternary complexes of aziridine⋯ammonia ruled by hydrogen bond strength

Oliveira

Araújo

2011

J Mol Model

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B3LYP calculations, ChelpG atomic charges, and quantum theory of atoms in molecules (QTAIM) integrations were used to investigate the binary (1:1) and ternary (1:2) hydrogen-bonded complexes formed by aziridine (1) and ammonia (2). In a series of analysis, geometry data, electronic parameters, vibrational oscillators, and topological descriptors were used to evaluate hydrogen bond strength, and additionally to determine the more prominent molecular deformations upon the formation of C(2)H(5)N···NH(3) (1:1) and C(2)H(5)N···2NH(3) (1:2) systems. Taking a spectroscopic viewpoint, results obtained from analysis of the harmonic infrared spectrum were examined. From these, new vibrational modes and red- and blue-shifts related to the stretch frequencies of either donors or acceptors of protons were identified. Furthermore, the molecular topology of the electronic density modeled in accord with QTAIM was absolutely critical in defining bond critical points (BCP) and ring critical points (RCP) on the heterocyclic structures. Taking all the results together allowed us to identify and characterize all the N···H hydrogen bonds, as well as the strain ring of the aziridine and its stability.

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An MP2 and DFT study of heterocyclic hydrogen complexes CnHmYHX with n=2, m=4 or 5, Y=O, S or N and X=F or Cl

Cited by 27 publications

References 14 publications

A computational study on the nature of the halogen bond between sulfides and dihalogen molecules

A computational study on the nature of the halogen bond between sulfides and dihalogen molecules

Evidence for blue-shifting and red-shifting effects in the C2H4···HCF3, C2H3(CH3)···HCF3 and C2H2(CH3)2···HCF3 complexes: π and improper-π hydrogen bonds

Theoretical aspects of binary and ternary complexes of aziridine⋯ammonia ruled by hydrogen bond strength

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