A Gate to Organokrypton Chemistry:  HKrCCH

Khriachtchev, Leonid; Tanskanen, Hanna; Cohen, Arik; Gerber, R. Benny; Lundell, Jan; Pettersson, Mika; Kiljunen, and Harri; Räsänen, Markku

doi:10.1021/ja0355269

Cited by 157 publications

(159 citation statements)

References 18 publications

(35 reference statements)

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“…10 The coupled cluster method (CCSD(T) version), which re quires considerable computational resources, allows much better agreement with experimental data on the vibra tional frequencies of molecules to be attained using the same basis set, 6,8 but can (at its best) provide only qualita tive agreement for radicals. 8, 27 In this work we performed calculations using a method based on scalar relativistic density functional theory (DFT) including solution of the vibrational problem in the harmonic approximation and with allowance for anharmonicity. First of all, this method was evaluated taking HXeCCH molecule as an example.…”

Section: Resultsmentioning

confidence: 99%

“…More recently, we 9 and other re searchers 10 simultaneously and independently obtained the first representative of this type of compounds, namely, HXeCCH (product of xenon insertion into acetylene mol ecule) and then identification of HKrCCH molecule was reported. 11 According to calculations, the dissociation energy of HXeCCH molecule into fragments can be as high as 1.5 eV, 8 which means that, in principle, this com pound can be stable at rather high temperatures.…”

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confidence: 99%

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Chemical reactions in the xenon-acetylene systems irradiated with fast electrons at 16 K: formation of xenon-containing molecules and radicals

et al. 2005

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The formation of HXeCCH molecules and HXeCC • radicals resulting from chemical reactions in solid xenon-acetylene systems irradiated with fast electrons was studied by low temperature IR and EPR spectroscopies. The data obtained confirm the assignment of an absorption band with maximum at 1478 cm -1 to the H-Xe stretching vibrations in the HXeCC • radical. Relativistic density functional calculations with inclusion of anharmonic corrections permit a quantitative description of the vibrational spectra of xenon containing molecules and radicals. Preliminary experimental and computational data on the magnetic resonance param eters of the HXeCC • radical were obtained. This radical is characterized by large hyperfine coupling constants with magnetic nuclei of the xenon isotopes.Rare gas hydrides (compounds of the HRgX type, where Rg is the rare gas atom and X is an atom or atomic group with sufficient electronegativity) were first identi fied in 1995. 1,2 The existence of such molecules was un expected and attracted considerable attention of experi mentalists and theoreticians. The nature of chemical bonding in the new compounds, criteria for their stability, and their properties are of great interest for chemistry. Our EPR and IR spectoscopy studies showed that the formation of HRgX molecules is due to reactions of mo bile H atoms in rare gas matrices. 3,4 This mechanism was also independently confirmed by other researchers. 5 Since then more than ten HRgX compounds were obtained, including the first neutral chemical compound of argon HArF. 6,7 A general procedure for preparing the HRgX (Rg = Xe, Kr) compounds involves dissociation of the precursor molecules HX in the solid rare gas matrix at low temperature (<20 K) followed by formation of the HRgX molecules as a result of thermal reactions proceeding on annealing of samples to the diffusion temperature of H atoms (40-45 K in xenon or 30-32 K in crypton). Dissociation of the HX molecules can be attained by ex posing to UV light 1,2 or by irradiation with fast elec trons. 3,4 All HRgX molecules correspond to metastable states (local minima) with energies lying 3-5 eV higher than the energies of the global minima corresponding to the HX molecules. 6 However, the new molecules are stable enough to have almost infinite lifetimes under the low temperature matrix isolation conditions. Identification of the HRgX molecules is facilitated by the fact that the IR absorption bands corresponding to the H-Rg stretching vibrations are characterized by extremely high intensities (in some cases, they are an order of magnitude more intense than the corresponding HX bands) due to very large dipole moments of transitions.The formation of organic molecules representing prod ucts of insertion of rare gas atoms into the C-H and O-H bonds is of particular interest. Recently, 8 the possi bility for a number of metastable compounds of the HXeR and HXeOR (R is an organic radical) types to exist was predicted theoretically. More recently, we 9 and other re searchers 10 simultaneously and ind...

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

Chemical reactions in the xenon-acetylene systems irradiated with fast electrons at 16 K: formation of xenon-containing molecules and radicals

et al. 2005

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“…The bond distances of the HKrCCH monomer agree with the previous MP2 calculations. 5 The B3LYP functional shows a shorter H-Kr bond and a longer Kr-C bond in HKrCCH compared with the CCSD(T) values. As expected, the MP2 method leads to shorter bonds compared with the CCSD(T) values.…”

Section: Quantum-chemical Calculationsmentioning

confidence: 87%

Matrix-isolation and computational study of the HKrCCH⋯HCCH complex

et al. 2015

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The HKrCCH/HCCH complex is identified in a Kr matrix with the H-Kr stretching bands at 1316.5 and 1305 cm À1. The monomer-to-complex shift of the H-Kr stretching mode is about +60 cm À1 , which is significantly larger than that reported previously for the HXeCCH/HCCH complex in a Xe matrix (about +25 cm À1 ). The HKrCCH/HCCH complex in a Kr matrix is formed at $40 K via the attachment of mobile acetylene molecules to the HKrCCH monomers formed at somewhat lower annealing temperatures upon thermally-induced mobility of H atoms ($30 K). The same mechanism was previously proposed for the formation of the HXeCCH/HCCH complex in a Xe matrix. The assignment of the HKrCCH/HCCH complex is fully supported by the quantum chemical calculations. The experimental shift of the H-Kr stretching mode is comparable with the computational predictions (+46.6, +66.0, and +83.2 cm À1 at the B3LYP, MP2, and CCSD(T) levels of theory, respectively), which are also bigger that the calculated shift in the HXeCCH/HCCH complex. These results confirm that the complexation effect is bigger for less stable noble-gas hydrides.

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“…1) and, by now, more than 30 compounds of this type have already been reported, [2][3][4][5][6][7][8] including an argon molecule HArF. 9 We can also mention the preparation and identication of organokrypton (HKrCCH and HKrC 4 H) 10,11 and organoxenon (HXeCCH, HXeCC, HXeCCXeH and HXeC 4 H) [11][12][13] hydrides. Matrix isolation is an ideal tool to study non-covalent interactions.…”

Section: Introductionmentioning

confidence: 99%