Inverse hydrogen bonds between XeH2 and hydride and fluoride derivatives of Li, Be, Na and Mg

Blanco, Fernando; Solimannejad, Mohammad; Alkorta, Ibón; Elguero, José

doi:10.1007/s00214-008-0462-3

Cited by 14 publications

(9 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The calculations were performed by using the density functional method B3LYP [40] in conjunction with DGDZVP basis set [41,42] as implemented in the Gaussian 03 suite of programs. [43] For all optimized structures, frequency analyses at the same level of theory were used to assign them as genuine minima or transition structures on the potential-energy surface as well as to calculate zero-point vibrational energies.…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

Formation of Organoxenon Dications in the Reactions of Xenon with Dications Derived from Toluene

Zins

Milko

Schröder

et al. 2011

Chemistry A European J

View full text Add to dashboard Cite

The bimolecular reactivity of xenon with C(7)H(n)(2+) dications (n=6-8), generated by double ionization of toluene using both electrons and synchrotron radiation, is studied by means of a triple-quadrupole mass spectrometer. Under these experimental conditions, the formation of the organoxenon dications C(7)H(6)Xe(2+) and C(7)H(7)Xe(2+) is observed to occur by termolecular collisional stabilization. Detailed experimental and theoretical studies show that the formation of C(7)H(6)Xe(2+)+H(2) from doubly ionized toluene (C(7)H(8)(2+)) and xenon occurs as a slightly endothermic, direct substitution of dihydrogen by the rare gas with an expansion to a seven-membered ring structure as the crucial step. For the most stable isomer of C(7)H(6)Xe(2+), an adduct between the cycloheptatrienyldiene dication and xenon, the computed binding energy of 1.36 eV reaches the strength of (weak) covalent bonds. Accordingly, electrophiles derived from carbenes might be particularly promising candidates in the search for new rare-gas compounds.

show abstract

Section: Wwwchemeurjorgmentioning

confidence: 99%

Formation of Organoxenon Dications in the Reactions of Xenon with Dications Derived from Toluene

Zins

Milko

Schröder

et al. 2011

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…In order to obtain the exact binding energy, it is necessary to perform BSSE correction. As for SiH 4 ···BeH 2 complex, the E CP obtained at MP2/6-311++g(3df, 3pd) and MP2/augcc-pvtz levels (3.96 and 4.58 kJ mol 1 ) are apparently [9], which is mainly attributed to the fact that Si-H is a weaker IHB electron donor than Xe-H. The vibrational frequencies and IR intensities of Si-H3 and Me-H (Me=Na, Mg, Be) bonds of the monomers and the complexes calculated at MP2/6-311++g**, MP2/6-311++g (3df, 3pd) and MP2/aug-cc-pvtz levels are listed in Table 3.…”

Section: Ihbs Binding Energy and Vibrational Frequencymentioning

confidence: 87%

“…Table 2 shows that the IHB binding energies (E, E CP ) obtained by B3LYP method are always less than that obtained by MP2 method, but the results of the MP2/6-311++g(3df, 3pd) and MP2/aug-cc-pvtz computational levels are equivalent. B3LYP method can not acquire perfect results in investigating weak interaction systems [9,[23][24][25]. Therefore, it can be regarded that compared with B3LYP method, MP2 is a better theoretical method in binding energy calculation.…”

Section: Ihbs Binding Energy and Vibrational Frequencymentioning

confidence: 99%

“…An IHB interaction probably exists intermolecularly solely with given composing and charge distribution, so IHB systems are few reported. Though Rozas [7] reckoned that the studies on IHBs would catch up with those on HBs, the second case about IHBs had not been reported until 2008 [9], in which the IHBs between XeH 2 and hydride and fluoride derivatives of Li, Be, Na and Mg were discussed. In general, IHBs are not given adequate interest and attention, Scheme 1 The transfer direction of electrons.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Inverse hydrogen bonds between SiH4 and hydrides of Na, Mg and Be

et al. 2011

View full text Add to dashboard Cite

The optimized geometries of the three complexes between MeH n (Me=Na, Mg, Be; n=1 or 2) and SiH 4 have been calculated at the B3LYP/6-311++g**, MP2/6-311++g(3df,3pd) and MP2/aug-cc-pvtz levels, respectively. The red-shift inverse hydrogen bonds (IHBs) based on Si-H, an electron donor, were reported. The calculated binding energies with basis set super-position error (BSSE) correction of the three complexes are 5.98, 8.65 and 3.96 kJ mol 1 (MP2/6-311++g(3df, 3pd)), respectively, which agree with the results obtained via MP2/aug-cc-pvtz (6.18, 9.12 and 4.28 kJ mol 1 , respectively). The relative stabilities of the three complexes are in the order of SiH 4 ···MgH 2 > SiH 4 ···NaH > SiH 4 ···BeH 2 . Natural bond orbital theory (NBO) analysis and the chemical shift calculation of the related atoms revealed that the charges flow from SiH 4 to MeH n and the chemical shifts of the interacting H shift to downfield. Here, the Si1-H3 of SiH 4 acts as both a bond hydrogen donor and an electron donor. Therefore, compared with conventional hydrogen bonds, they formed IHB complexes. Atoms in molecules (AIM) theory have been used to investigate the topological properties of the critical points in the three IHB structures.SiH 4 , metal hydride, inverse hydrogen bond, electron density topological property

show abstract

“…and H -is mainly ionic [32]. Due to the negative partial charge on the hydrogen atoms, several theoretical works have verified that the HXeH can provide its electron and further formed the dihydrogen bond or hydride bond interactions [33][34][35][36][37]. There are also some theoretical works that have been devoted to this compound due to its properties for formation of halogen bonding [38,39].…”

Section: Introductionmentioning

confidence: 99%

An ab initio investigation of chalcogen–hydride interactions involving HXeH as a chalcogen bond acceptor

2015

View full text Add to dashboard Cite

This work presents an ab initio study on chalcogen-hydride interactions in several binary complexes of chalcogen-containing molecules with HXeH. The geometries, H-Xe stretching frequencies and interaction energies of XCYÁÁÁHXeH binary complexes are investigated at MP2/aug-cc-pVTZ and CCSD(T)/aug-cc-pVTZ levels of theory, where X = O, S, Se, Te and Y = S, Se, Te. For each XCYÁÁÁHXeH complex, a chalcogen-hydride bond is formed between the negatively charged hydrogen atom of the HXeH molecule and the most positive electrostatic potential region (r-hole) on the surface of the interacting atom Y. Upon complex formation, a notable blue shift is found for the H-Xe stretch vibration. This result reveals that there is a stronger H -(XeH) ? ion-pair character in XCYÁÁÁHXeH complexes than in free HXeH molecule. In order to shed light on the origin of the chalcogen-hydride interactions, molecular electrostatic potential, quantum theory of atoms in molecules and interaction energy decomposition analyses are performed. Cooperative effects between a conventional chalcogen bond and the chalcogen-hydride interaction in OCYÁÁÁOCYÁÁÁHXeH complexes are also investigated.

show abstract

Inverse hydrogen bonds between XeH2 and hydride and fluoride derivatives of Li, Be, Na and Mg

Cited by 14 publications

References 41 publications

Formation of Organoxenon Dications in the Reactions of Xenon with Dications Derived from Toluene

Formation of Organoxenon Dications in the Reactions of Xenon with Dications Derived from Toluene

Inverse hydrogen bonds between SiH4 and hydrides of Na, Mg and Be

An ab initio investigation of chalcogen–hydride interactions involving HXeH as a chalcogen bond acceptor

Contact Info

Product

Resources

About