Siliciumverbindungen von Neon und Argon

Roithová, Jana; Schröder, Detlef

doi:10.1002/ange.200903706

Cited by 9 publications

(1 citation statement)

References 34 publications

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“…[2][3][4][5][6][7][8] The noble gas hydrides HNgY (Ng = noble gas atom; Y = electronegative fragment) constitute, in particular, a important part of modern noble gas chemistry. [9,10] These molecules are prepared by photodissociation of HY in a cold Ng matrix and subsequent mobilization of the hydrogen atoms.…”

Section: Introductionmentioning

confidence: 99%

Stabilization of HHeF by Complexation: Is it a Really Viable Strategy?

Giordani

Antoniotti

Grandinetti

2010

Chemistry A European J

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Ab initio calculations at the MP2 and CCSD(T) levels of theory have disclosed the conceivable existence of fluorine-coordinated complexes of HHeF with alkali-metal ions and molecules M(+) (M(+)=Li(+)-Cs(+)), M(+)-OH(2), M(+)-NH(3) (M(+)=Li(+), Na(+)), and MX (M=Li, Na; X=F, Cl, Br). All these ligands L induce a shortening of the H-He distance and a lengthening of the He-F distance accompanied by consistent blue- and redshifts, respectively, of the H-He and He-F stretching modes. These structural effects are qualitatively similar to those predicted for other investigated complexes of the noble gas hydrides HNgY, but are quantitatively more pronounced. For example, the blueshifts of the H-He stretching mode are exceptionally large, ranging between around 750 and 1000 cm(-1). The interactions of HHeF with the ligands investigated herein also enhance the (HHe)(+)F(-) dipole character and produce large complexation energies of around 20-60 kcal mol(-1). Most of the HHeF-L complexes are indeed so stable that the three-body dissociation of HHeF into H+He+F, exothermic by around 25-30 kcal mol(-1), becomes endothermic. This effect is, however, accompanied by a strong decrease in the H-He-F bending barrier. The complexation energies, DeltaE, and the bending barriers, E*, are, in particular, related by the inverse relationship E*(kcal mol(-1))=6.9exp[-0.041DeltaE(kcal mol(-1))]. Therefore the HHeF-L complexes, which are definitely stable with respect to H+He+F+L (DeltaE approximately 25-30 kcal mol(-1)), are predicted to have bending barriers of only 0.5-2 kcal mol(-1). Overall, our calculations cast doubt on the conceivable stabilization of HHeF by complexation.

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Section: Introductionmentioning

confidence: 99%

Stabilization of HHeF by Complexation: Is it a Really Viable Strategy?

Giordani

Antoniotti

Grandinetti

2010

Chemistry A European J

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Fast and Efficient Fluorination of Small Molecules by SF₄²⁺

2010

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Fast and Efficient Fluorination of Small Molecules by SF₄²⁺

2010

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Doubly charged, highly efficient: The use of a mass spectrometric technique specifically designed to monitor the reactions of dications has revealed that gaseous SF42+ is a powerful fluorinating agent. The fluorination of different classes of compounds (Ar, CO, CH4, C2H4, and H2) has been efficiently achieved in the gas phase (see picture). Of particular note is the formation of CF bonds in the reactions with organic compounds.

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Siliciumverbindungen von Neon und Argon

Cited by 9 publications

References 34 publications

Stabilization of HHeF by Complexation: Is it a Really Viable Strategy?

Stabilization of HHeF by Complexation: Is it a Really Viable Strategy?

Fast and Efficient Fluorination of Small Molecules by SF₄²⁺

Fast and Efficient Fluorination of Small Molecules by SF₄²⁺

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Siliciumverbindungen von Neon und Argon

Cited by 9 publications

References 34 publications

Stabilization of HHeF by Complexation: Is it a Really Viable Strategy?

Stabilization of HHeF by Complexation: Is it a Really Viable Strategy?

Fast and Efficient Fluorination of Small Molecules by SF42+

Fast and Efficient Fluorination of Small Molecules by SF42+

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Product

Resources

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Fast and Efficient Fluorination of Small Molecules by SF₄²⁺

Fast and Efficient Fluorination of Small Molecules by SF₄²⁺