The gas phase structure of arsenic dichloride trifluoride and a vibrational analysis of AsClnF5-n (n = 1-5)

Minkwitz, R.; Prenzel, H.; Schardey, A.; Oberhammer, Heinz

doi:10.1021/ic00263a035

Cited by 9 publications

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“…The gas-phase structure of AsCl 2 F 3 has been determined experimentally by electron diffraction. [5] AsCl 2 Br and AsClBr 2 are the only reported mixed halogen compounds of arsenic in the ϩ3 oxidation state. Müller et al reported on the vibrational spectroscopic investigations of these mixed bromochloroarsanes.…”

Section: Introductionmentioning

confidence: 97%

“…[2] AsCl 2 F 3 [3] and AsClF 4 [4] were formed by intermolecular ligand exchange in the gas phase at 173 K. These compounds are extremely unstable due to dismutation under halogen exchange in the respective halides. [5] AsCl 2 F 3 is the only structurally characterised mixed halogen compound of arsenic. The gas-phase structure of AsCl 2 F 3 has been determined experimentally by electron diffraction.…”

Section: Introductionmentioning

confidence: 99%

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Mixed Chloride/Azide Complexes of Arsenic and Antimony

Klapötke

Nöth

Schütt

et al. 2002

Eur. J. Inorg. Chem.

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The Lewis acid base complexes AsCl(N 3 ) 2 ·pyridine and SbCl 2 N 3 ·2 pyridine were prepared. The products formed were characterised by Raman, IR and NMR spectroscopy. Density functional theory (B3LYP) was applied to calculate structural and vibrational data. Vibrational assignments of the normal modes for the isolated compounds were made on the basis of their vibrational spectra in comparison with com-

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Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Mixed Chloride/Azide Complexes of Arsenic and Antimony

Klapötke

Nöth

Schütt

et al. 2002

Eur. J. Inorg. Chem.

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“…However, only the preparation of AsBr 4 + [Al(OR) 4 ] − proceeded as indicated in eqn. (12). After precipitation of AgBr and low-temperature work-up we isolated slightly yellowish crystals in 54% yield.…”

Section: Reactions Ofmentioning

confidence: 95%

Preparation of stable AsBr₄⁺and I₂As–PI₃⁺salts. Why didn't we succeed to prepare AsI₄⁺and As₂X₅⁺? A combined experimental and theoretical study

Gonsior

Krossing

2005

Dalton Trans.

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In analogy to our successful "PX2+" insertion reactions, an "AsX2+" insertion route was explored to obtain new arsenic halogen cations. Two new salts were prepared: AsBr4+[Al(OR)4]-, starting from AsBr3, Br2 and Ag[Al(OR)4], and I2As-PI3+[Al(OR)]4 from AsI3, PI3 and Ag[Al(OR)4](R=C(CF3)3). The first cation is formally a product of an "AsBr2+" insertion into the Br2 molecule and the latter clearly a "PI2+" insertion into the As-I bond of the AsI3 molecule. Both compounds were characterized by IR and NMR spectroscopy, the first also by its X-ray structure. Reactions of Ag[Al(OR)4] with AsI3 do not lead to ionization and AgI formation but rather lead to a marginally stable Ag(AsI3)2+[Al(OR)]4 salt. Despite many attempts we failed to prepare other PX-cation analogues such as AsI4+, As2X5+ and P4AsX2+(X=Br, I). To explain these negative results the thermodynamics of the formation of EX2+, EX4+ and E2X5+(E = As, P; X = Br, I) was carefully analyzed with MP2/TZVPP calculations and inclusion of entropy and solvation effects. We show that As2Br5+ is in very rapid equilibrium with AsBr2+ and AsBr3(DeltaGo((CH2Cl2))=+30 kJ mol(-1)). The extremely reactive AsBr2+ cation available in the equilibrium accounts for the observed decomposition of the [Al(OR)4]- anion. By contrast, the stability of AsI3 against Ag[Al(OR)4] appears to be kinetic and, if prepared by a suitable route, As2I5+ would be expected to have a stability intermediate between the known P2I5+ and P2Br5+.

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ChemInform Abstract: Gas‐Phase Structure of AsCl2F3 and a Vibrational Analysis of AsClnF5‐n (n = 1‐5).

et al. 1987

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001ChemInform Abstract AsCl2F3 (I) has been isolated at -80 rc C after pyrolysis of AsCl4+AsF6-. AsCl3F2 is accessible by a gas-phase/solid reaction of (I) and CaCl2 and may be characterized by vibrational spectroscopy below -196 rc C. The analysis of the radial distribution curve of (I) confirms C2v symmetry with equatorial positions of the two Cl atoms. The angular distortions from the ideal trigonal bipyramid are small. The axial As-F bonds lengthen upon substitution of two equatorial fluorines by chlorines. The trends in the As-F and As-Cl bond lengths within the series of mixed chlorofluoroarsoranes are similar to those determined for the analogous phosphorane series.

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The gas phase structure of arsenic dichloride trifluoride and a vibrational analysis of AsClnF5-n (n = 1-5)

Cited by 9 publications

References 0 publications

Mixed Chloride/Azide Complexes of Arsenic and Antimony

Mixed Chloride/Azide Complexes of Arsenic and Antimony

Preparation of stable AsBr₄⁺and I₂As–PI₃⁺salts. Why didn't we succeed to prepare AsI₄⁺and As₂X₅⁺? A combined experimental and theoretical study

ChemInform Abstract: Gas‐Phase Structure of AsCl2F3 and a Vibrational Analysis of AsClnF5‐n (n = 1‐5).

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The gas phase structure of arsenic dichloride trifluoride and a vibrational analysis of AsClnF5-n (n = 1-5)

Cited by 9 publications

References 0 publications

Mixed Chloride/Azide Complexes of Arsenic and Antimony

Mixed Chloride/Azide Complexes of Arsenic and Antimony

Preparation of stable AsBr4+and I2As–PI3+salts. Why didn't we succeed to prepare AsI4+and As2X5+? A combined experimental and theoretical study

ChemInform Abstract: Gas‐Phase Structure of AsCl2F3 and a Vibrational Analysis of AsClnF5‐n (n = 1‐5).

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Preparation of stable AsBr₄⁺and I₂As–PI₃⁺salts. Why didn't we succeed to prepare AsI₄⁺and As₂X₅⁺? A combined experimental and theoretical study