On three-electron bonds and hydrogen bonds in the open-shell complexes [H2X2]+ for X = F, Cl, and Br

The [H2X2]+ (X = Cl, Br) formula could refer to two possible stable structures, namely, the hydrogen-bonded complex and the three-electron-bonded one. In contrary to the results published by other authors, we claim that for the F-type structures the hydrogen-bonded form is the only possible one and the [HFFH]+ complex is an artifact as its wave function is unstable. For all analyzed molecules, the IR anharmonic spectra have been simulated, which enabled a deeper analysis of other authors' published results of IR low-temperature matrix experiments. Topological atoms in molecules and electron localization function investigations have revealed that the nature of the bond in three-electron-bonded structures is similar to the covalent-depleted one in F2 or HOO molecules, but the effect of removing electrons from the bond area is stronger.     

The mechanism of C--X (X=F, Cl, Br, and I) bond activation in CX4 by a stabilized dialkylsilylene

The potential-energy surfaces for the abstraction and insertion reactions of dialkylsilylene with carbon tetrahalides (CX4) have been characterized in detail using density functional theory (B3LYP), including zero-point corrections. Four CX4 species, CF4, CCl(4), CBr4, and CI(4), were chosen as model reactants. The theoretical investigations described herein suggest that of the three possible reaction paths, the one-halogen-atom abstraction (X abstraction), the one-CX3-group abstraction (CX3 abstraction), and the insertion reaction, the X-abstraction reaction is the most favorable, with a very low activation energy. However, the insertion reaction can lead to the thermodynamically stable products. Moreover, for a given stable dialkylsilylene, the chemical reactivity has been found to increase in the order CF4相似文献   

Vibrational frequencies,force constants,coriolis constants,mean amplitudes and shrinkage effects for CH3CC-CCX (X = H,Cl, Br an

Normal coordinate analyses for methyldiacetylene and its 1-halo derivatives, CH₃CC-CCX (X = H, CI, Br or I), were performed on the basis of experimental vibrational frequencies not published previously. The molecules belong to a pyramidal-axial model of C_3v symmetry. Coriolis coupling constants of the E_a × E_b type are given. Also the mean amplitudes of vibration, perpendicular amplitude correction coefficients and shrinkage effects were calculated. The mean amplitudes are discussed in particular, and characteristic values for certain types of interatomic distances are deduced.     

Microwave spectra, geometries, and hyperfine constants of OCAgX (X = F, Cl, Br)

A pulsed jet cavity Fourier transform microwave spectrometer has been used to measure the rotational spectra of OCAgX (X = F, Cl, Br) in the frequency range 5-22 GHz. Metal atoms were generated via laser ablation and were allowed to react with CO and a halide precursor, prior to stabilization of the products within a supersonic jet of argon. These are the first experimental observations of OCAgF and OCAgBr, and the first high resolution spectroscopic study of OCAgCl. All three molecules are linear. Accurately determined rotational constants have been used to evaluate the various internuclear distances, which are found to be consistent with trends established for OCAuX and OCCuX species. The C-O distances are short, and the M-C distances are significantly longer than those in other molecules containing a metal-carbonyl bond. Precise values of centrifugal distortion constants and halogen nuclear quadrupole coupling constants have also been determined. The coupling constants are compared with the results of previous studies of OCCuX and OCAuX and are used to infer trends in the electron distributions of the molecules. Ab initio calculations have been performed and employed to predict the geometries, vibrational frequencies, and Mulliken valence orbital populations of the various species.     

Some measures for making halogen bonds stronger than hydrogen bonds in H2CS-HOX (X = F, Cl, and Br) complexes

The properties and applications of halogen bonds are dependent greatly on their strength. In this paper, we suggested some measures for enhancing the strength of the halogen bond relative to the hydrogen bond in the H(2)CS-HOX (X = F, Cl, and Br) system by means of quantum chemical calculations. It has been shown that with comparison to H(2)CO, the S electron donor in H(2)CS results in a smaller difference in strength for the Cl halogen bond and the corresponding hydrogen bond, and the Br halogen bond is even stronger than the hydrogen bond. The Li atom in LiHCS and methyl group in MeHCS cause an increase in the strength of halogen bonding and hydrogen bonding, but the former makes the halogen bond stronger and the latter makes the hydrogen bond stronger. In solvents, the halogen bond in the Br system is strong enough to compete with the hydrogen bond. The interaction nature and properties in these complexes have been analyzed with the natural bond orbital theory.     

The compounds KAs4O6 X (X=Cl,Br, I) and NH4As4O6 X (X=Br,I): Hydrothermal syntheses and structure determinations

The crystal structures of five isotypic hexagonal compounds with general formulaMAs₄O₆ X [M=K, NH₄;X=Cl, Br, I; space group: P622;Z=1] were determined from 370 single crystal X-ray data and refined toR values <0.05. The structure type is characterized by neutral charged [As₂O₃] sheets arranged parallel (00.1). The As atoms of neighbouring two sheets point to each other and the sheets are combined by interlayeredM andX atoms, respectively. TheM atoms are coordinated to twelve oxygen atoms, theX atoms are coordinated to twelve arsenic atoms. In both cases the coordination polyhedron is a hexagonal prism. The compounds were synthesized by thermal treatments of cubic As₂O₃ and potassium or ammonium haloids in a saturated aqueous solution of potassium acetate resp. ammonia [500 K, saturation vapour pressure].

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Die Verbindungen KAs₄O₆ X (X=Cl, Br, I) und NH₄As₄O₆ X (X=Br, I): Hydrothermalsynthese und Strukturbestimmung

Zusammenfassung Die Kristallstrukturen der fünf isotypen hexagonalen Verbindungen mit der allgemeinen FormelMAs₄O₆ X [M=K, NH₄;X=Cl, Br, I; Raumgruppe: P622;Z=1] wurden anhand von 370 Einkristall-Röntgendaten bestimmt und aufR-Werte <0.05 verfeinert. Der Strukturtyp ist ausgezeichnet durch neutrale [As₂O₃]-Schichten, die parallel (00.1) angeordnet sind. Die As-Atome zweier benachbarter Schichten weisen jeweils aufeinander zu, und die Schichten selbst werden durch zwischengelagerteM- bzw.X-Atome verbunden. DieM-Atome werden jeweils von zwölf O-Atomen, dieX-Atome von zwölf As-Atomen umgeben. Das Koordinationspolyeder ist in beiden Fällen ein hexagonales Primsa. Die einzelnen Verbindungen wurden unter Hydrothermalbedingungen aus kubischem As₂O₃ und dem jeweiligen Kalium- oder Ammoniumhalogenid in einer gesättigten wäßrigen Lösung von Kaliumacetat bzw. Ammoniak synthetisiert (500 K, Sättigungsdampfdruck).

     

GeH4与HX(X＝F,Cl,Br)间二氢键复合物的理论研究

对GeH4与HX形成的二氢键复合物的结构特征及本质进行了探讨.在MP2/6-311 ++G(3 d,3p)水平优化、频率验证得到复合物的分子结构,通过分子的几何参数及电子密度拓扑分析,确认GeH4与卤化氢已形成了二氢键复合物.MP2/6-311 ++ G(3d,3p)水平下进行BSSE校正后的结合能为3.281到4.5...     

A CNDO study of the electronic structure of oxyanions XO4n− with X = Si,P, S,Cl, Ge,As, Se and Br

The orbital order, the bonding properties of the orbitals and the orbital populations are discussed. It is concluded that the orbital order in the valence shell in all the ions is 1a₁, 1t₂, 2a₁, 2t₂, 1e, 3t₂ and 1t₁. The results are compared when possible with experimental data and ab initio results.     

Ab initio determination of molecular geometries and vibrational frequencies of CX3 COOH (X=H, F, Cl, Br)

Using Gaussian 03 Revision C.02 version of the quantum chemical program ab initio and DFT computations have been carried out at the rhf/6-31+g*, b3lyp/6-31+g*, b3lyp/6-31++g** and b3lyp/6-311++g** levels to compute optimized geometries, harmonic vibrational frequencies along with intensities in IR and Raman spectra and atomic charges for the acetic (ethanoic) acid and its 1,1,1-tri-halo (fluoro, chloro and bromo) derivatives. The optimized molecular structures for all the four molecules are found to possess Cs point group symmetry. The symmetric stretching mode is found to have lowest magnitude of the three CX3 stretching modes for all the four molecules, whereas the symmetric deformation mode is found to have the lowest magnitude for EA and TFEA and the highest magnitude for TCEA and TBEA. The parallel rocking mode of the CX3 group is found to have lower magnitude than the perpendicular rocking mode for EA and TFEA where reverse is found for TCEA and TBEA. The modes of the COOH group are substituent sensitive except the OH stretching mode. Moreover, the maximum effect is found for the TFEA molecule. The CF3 group is found to have the characteristic frequencies as 235-505, 787, 1150-1190 and 1400 cm(-1) which are due to the modes delta s(CF3), nu s(CF3), nu as(CF3) and nu(C-CF3), respectively.     

Halogen-hydride interaction between Z-X (Z = CN, NC; X = F, Cl, Br) and H-Mg-Y (Y = H, F, Cl, Br, CH3)

Halogen-hydride interactions between Z-X (Z = CN, NC and X = F, Cl, Br) as halogen donor and H-Mg-Y (Y = H, F, Cl, Br, CH(3)) as electron donor have been investigated through the use of Becke three-parameter hybrid exchange with Lee-Yang-Parr correlation (B3LYP), second-order M?ller-Plesset perturbation theory (MP2), and coupled-cluster single and double excitation (with triple excitations) [CCSD(T)] approaches. Geometry changes during the halogen-hydride interaction are accompanied by a mutual polarization of both partners with some charge transfer occurring from the electron donor subunit. Interaction energies computed at MP2 level vary from -1.23 to -2.99 kJ/mol for Z-F···H-Mg-Y complexes, indicating that the fluorine interactions are relatively very weak but not negligible. Instead, for chlorine- and bromine-containing complexes the interaction energies span from -5.78 to a maximum of -26.42 kJ/mol, which intimate that the interactions are comparable to conventional hydrogen bonding. Moreover, the calculated interaction energy was found to increase in magnitude with increasing positive electrostatic potential on the extension of Z-X bond. Analysis of geometric, vibrational frequency shift and the interaction energies indicates that, depending on the halogen, CN-X···H interactions are about 1.3-2.0 times stronger than NC-X···H interactions in which the halogen bonds to carbon. We also identified a clear dependence of the halogen-hydride bond strength on the electron-donating or -withdrawing effect of the substituent in the H-Mg-Y subunits. Furthermore, the electronic and structural properties of the resulting complexes have been unveiled by means of the atoms in molecules (AIM) and natural bond orbital (NBO) analyses. Finally, several correlative relationships between interaction energies and various properties such as binding distance, frequency shift, molecular electrostatic potential, and intermolecular density at bond critical point have been checked for all studied systems.     

A theoretical study of the CX2N radicals (X = F, Cl, Br): the effect of halogen substitution on structure, isomerization, and energetics

Structural isomers of the CX(2)N radicals, where X = F, Cl, and Br, have been investigated at high level of theory, i.e., using the coupled-cluster method in conjunction with correlation-consistent basis sets ranging in size from triple- to sextuple-zeta. Extrapolation to the complete basis-set limit as well as core-correlation effects and inclusion of higher excitations in the cluster operator have been considered for accurately evaluating geometries and energies. The effect of halogen substitution on molecular structure, isomer stability, and dissociation energy is addressed; in particular, only the F(2)CN, Cl(2)CN, Br(2)CN, and F(2)NC radicals of C(2V) symmetry are predicted to be stable with respect to dissociation.     

Structures and Aromaticity of Three-membered BeXP （X = C,Si, Ge） and CYP （Y = O,S, Se） Rings

Three-membered BeXP （X = C, Si, Ge） and CYP （Y = O, S, Se） rings are theoretically investigated using density functional theory （DFT） methods at the B3LYP/6-311＋G^＊ and B3PW91/6-311＋G^＊ levels of theory. The research results show that the size of atoms has a great influence on the structural stability of these species. The wiberg bond indexs （WBIs） suggest the existence of delocalization in these structures. Negative nucleus-independent chemical shift （NICS） values for these species indicate that a strong ring current exists in these three-membered structures （Cs symmetry）. A detailed molecular orbital （MO） analysis further reveals that a delocalized π MO strengthens the structural stability and makes these species show strong aromatic characters.     

Products, rate constants and mechanisms of gas-phase reactions of CX(3)(+), CX(2)(+), CX(+) (X = F and/or Cl) and Cl(+) with 1,1,1- and 1,1,2-trichlorotrifluoroethane.

The gas-phase ion chemistry of 1,1,1- and 1,1,2-trichlorotrifluoroethane was investigated with an ion trap mass spectrometer. Following electron ionization both compounds (M) fragment to [M - Cl](+), CX(3)(+), CX(2)(+), CX(+) (X = F and/or Cl) and Cl(+). The reactivity of each of these fragments towards their neutral precursors was studied to obtain product and kinetic data. Whereas [M - Cl](+), CCl(3)(+) and CCl(2)F(+) cations are unreactive under the experimental conditions used, all other species react via halide abstraction to give [M - Cl](+) and, to a far lesser extent, [M - F](+). In addition, CX(2)(+) ions form CClX(2)(+) in a process which formally amounts to chlorine atom abstraction, but more likely involves chloride ion abstraction followed by charge transfer. CX(+) ions also form minor amounts of CX(3)(+) product ions, possibly via chloride abstraction followed by or concerted with dihalocarbene elimination from the (incipient) [M - Cl](+) ion. Trivalent carbenium ions are less reactive than divalent species, which in turn are less reactive than the monovalent ions (reaction efficiencies are given in parentheses): CF(3)(+)(0.70) < CF(2)(+)(0.78) < CF(+)(0.96). More interestingly, within each family of ions reactivity increases with the number of fluorine substituents (e.g. CF(2)(+) > CFCl(+) > CCl(2)(+) and CF(+) > CCl(+)), i.e. reactivity increases with the ion thermochemical stability, as measured by available standard free enthalpies of formation. Evaluation of the energetics involved shows that reactions are largely driven by the stability of the neutrals more than of the ions. Finally, the products observed in the reaction of Cl(+) are attributed to ionization of the neutral via charge transfer and fragmentation.     

Relationship between the bond lengths in N-H...N,O-H...O,F-H...F,and Cl-H...Cl hydrogen bridges

The applicability of the equation $ e^{ - ((r_1 - r_0 )/b)^{5/3} } + e^{ - ((r_2 - r_0 )/b)^{5/3} } = 1 $ e^{ - ((r_1 - r_0 )/b)^{5/3} } + e^{ - ((r_2 - r_0 )/b)^{5/3} } = 1 has been studied. The equation defines the relationship between the experimental values of the covalent (r ₁) and hydrogen (r ₂) bond lengths in O-H...O bridges for describing the relation between the experimental interatomic distances in N-H...N bridges and the parameters of X-H...X fragments (X = O, N, F, Cl) calculated by the density functional method (B3LYP/6-31++G(d,p)) for neutral, positive, and negative molecular complexes. Here r ₀ is the mean value of the X-H bond length in free molecules; r _sym is the X...H distance in the symmetrical bridge; and b is the coefficient defined by the equation b = (r _sym − r ₀)/(ln2)^3/5. This equation allows us to adequately describe the relationships between bond lengths in nearly linear hydrogen bridges formed by oxygen, nitrogen, fluorine, and chlorine atoms. It is thus universal and can be used in studies of a wide range of substances.     

XHn型气相分子的合成技术

近年来，分了局域模振动的光谱理论研究已成为分子光谱学引人入胜的前沿领域[1]，而研究分子局域模振动最具说服力的分子对象就是XHn型气相分子。Si、Ge、Sn、S、Se、Te、P、As、Sb等元素的氢化物都很活泼，容易分解，大部分属剧毒气体，必须在通风橱中处理这类气体。早期文献中介绍XHn型分子的合成比较多[2～4]，但适合普通实验室设备的简单、实用、安全的合成方法并不多见。     

XH3Y（X=C,Si,Ge;Y=Cl,Br,I,D）型气相分子合成技术

ＸＨ３Ｙ（Ｘ＝Ｃ，Ｓｉ，Ｇｅ；Ｙ＝Ｃｌ，Ｂｒ，Ｉ，Ｄ）型气相分子合成技术周泽义邓珂（中国科技大学选键化学开放实验室合肥２３００２６）谢立（安徽省计量测试研究所合肥２３００２２）关键词气相分子真空合成正交表中图分类号Ｏ６２１．２５５１ＩＶＸ的Ｃ、Ｓｉ、...     

Darstellung und spektroskopische Charakterisierung der Fluorphosphonium-Salze X2FPSCH3+MF6− (X = Br,Cl; M = As,Sb) und XF2PSCH3+SbF6− (X = Br,Cl, F)

Preparation and Spectroscopic Characterization of the Fluorophosphonium Salts X₂FPSCH₃⁺MF₆^? (X = Br, Cl; M = As, Sb) and XF₂PSCH₃⁺SbF₆^? (X = Br, Cl, F) The preparation of the fluorophosphonium salts X₂FPSCH₃⁺MF₆^? (X = Br, Cl; M = As, Sb) and XF₂PSCH₃⁺SbF₆^? (X = Br, Cl, F) by methylation of the corresponding thiophosphorylhalides in the system CH₃F/SO₂/MF₅ (M = As, Sb) is reported. The new salts are characterized by their vibrational and NMR spectra.     

Double carbon-halogen bond in the compounds H2CX+, H2CCX+, and H2BCX (X = F, Cl)

The structure of formaldehyde and ketene analogs H₂CX and H₂CCX (X = O, F⁺, Ne²⁺, S, Cl⁺, Ar²⁺), and also of boron-containing compounds H₂BCX (X = F, Cl), was studied by ab initio [CCD(full)/6-311+G**] and DFT (B3LYP/6-311+G**) calculations. In all the halogen-containing species except H₂BCF, a double carbon-halogen bond is formed.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 10, 2004, pp. 1649–1654.Original Russian Text Copyright © 2004 by Minyaev, Gribanova.This revised version was published online in April 2005 with a corrected cover date.