A fluorine magnetic resonance study of the solid addition compounds SF4•AsF5 and IF7•AsF5

Barr, M. R.; Dunell, B. A.

doi:10.1139/v70-147

Cited by 9 publications

(4 citation statements)

References 2 publications

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“…The limiting low temperature second moment data (77 to 200 K ) have been interpreted in terms of a static structure (7). This is consistent with our analysis and calculations.…”

Section: Low Temperature Phasesupporting

confidence: 90%

Ionic reorientations and phase transition in solid IF₆AsF₆

Albert¹,

Ripmeester²

1988

Can. J. Chem.

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. 66, 3153 (1988)."F static and rotating frame spin-lattice relaxation times (TI and Tlp) as well as broadline NMR studies have been carried out on solid IF6AsF6 between 213 and 393 K. From the TI-and TIP-temperature behaviour, we inferred a phase transition at 350(?2) K and a supercooled high temperature phase. In both phases the second moments are consistent with a model where both IF6' and AsF6-reorient about random axes. The TI and TIP data in the low temperature phase can be interpreted in terms of a single frequency factor TO = 3.15(?0.2) X 10-16 s and activation energy E, = 10.4(?0.4) kcal/mol for both cation and anion reorientation. At the temperature of the phase transition the ionic-reorientational frequencies become faster by -2 orders of magnitude. In the high temperature phase TI and TIP are essentially independent of temperature which may be associated with a spin-rotation relaxation mechanism.SHMUEL ALBERT et JOHN A. RIPMEESTER. Can. J. Chem. 66, 3153 (1988).Operant a des tempkratures allant de 21 3 a 393 K, on a determink les temps de relaxation spin-rkseau statiques et de rotation du I9F (TI et Tip) et on a effectuk des etudes rmn a bandes larges sur le IF6AsF6. En se basant sur le comportement des valeurs de TI et T en fonction de la temperature, on en a dkduit qu'il existe une phase de transition a 350(?2) K ainsi qu'une phase a une ' P temperature de surfusion. Dans chacune de ces phases, les moments secondaires sont en accord avec un modkle dans lequel les deux ions IF6' ainsi que AsF6-se rkorientent autour d'axes au hasard. Onpeut interprkter les donnkes relatives aux TI et TIP de la phase a basse temperature en fonction d'un facteur de frequence unique, TO = 3,15(?0,2) x 10-l6 s et une knergie d'activation E, = 10,4(*0,4) kcal/mol pour les rkorientations tant du cation que de l'anion. A la temperature de la transition de phase, les frkquences de la reorientation ionique augmentent par un facteur d'environ 100. Dans la phase a haute tempkrature, les valeurs de T1 et Tlp sont essentiellement independantes de la tempkrature qui pourrait Ctre associee avec un mecanisme de relaxation spin-rotation.[Traduit par la revue]

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“…The limiting low temperature second moment data (77 to 200 K ) have been interpreted in terms of a static structure (7). This is consistent with our analysis and calculations.…”

Section: Low Temperature Phasesupporting

confidence: 90%

Ionic reorientations and phase transition in solid IF₆AsF₆

Albert¹,

Ripmeester²

1988

Can. J. Chem.

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“…A more detailed study at frequencies up to 94.1 MHz showed resolved peaks for F in AsFe-and F in IF6+. 10 In this paper we present the results of a Raman study of IF7, as a liquid and dissolved in FIF, and the 19F nmr spectrum of IFe+ in HF. The Raman spectrum of IFe+AsFe-in HF has already been reported,7 so no further work was carried out on it.…”

mentioning

confidence: 99%

Spectroscopic study of IF7 and IF6+ in anhydrous hydrogen fluoride

Brownstein¹,

Selig²

1972

Inorg. Chem.

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“…The SF 3 + cation has been previously characterized as its AsF 6 − , ,− SbF 6 − , , PF 6 − , , BF 4 − , ,− and GeF 6 − salts. A series of mixed CF 3 /F adduct cations, [(CF 3 ) n (F) 3− n S---NSF 3 ][AsF 6 ] ( n = 0−2), has been studied by 19 F NMR spectroscopy in SO 2 solvent at temperatures below −30 °C where the cations corresponding to n = 0 or 1 are labile and weakly coordinated .…”

Section: Resultsmentioning

confidence: 99%

On the Reactivity of F₃S≡NXeF⁺: Syntheses and Structural Characterizations of [F₄S═N−Xe---N≡SF₃][AsF₆], a Rare Example of a N−Xe−N Linkage, and [F₃S(N≡SF₃)₂][AsF₆]

Smith

Schrobilgen

2009

Inorg. Chem.

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The F(4)S=N-Xe---N[triple bond]SF(3)(+) cation has been synthesized as the AsF(6)(-) salt by rearrangement of [F(3)S[triple bond]NXeF][AsF(6)] in N[triple bond]SF(3) solvent at 0 degrees C. Deep yellow [F(4)S=N-Xe---N[triple bond]SF(3)][AsF(6)], which crystallized from a N[triple bond]SF(3) solution at -10 degrees C, was characterized by Raman spectroscopy (-160 degrees C) and by single-crystal X-ray diffraction (-173 degrees C). The Xe-N bond length (2.079(3) A) of the F(4)S=N-Xe---N[triple bond]SF(3)(+) cation is among the shortest Xe-N bonds presently known. The F(4)S=NXe(+) cation interacts with N[triple bond]SF(3) by means of a Xe---N donor-acceptor bond (2.583(3) A) that is significantly longer than the primary Xe-N bond (2.079(3)A) but significantly shorter than the sum of the Xe and N van der Waals radii (3.71 A). The F(4)S=N-Xe---N[triple bond]SF(3)(+) cation undergoes a redox decomposition in N[triple bond]SF(3) at 0 degrees C, forming [F(3)S(N[triple bond]SF(3))(2)][AsF(6)], cis-N(2)F(2), and Xe, which were characterized by low-temperature Raman spectroscopy in the solid state and by (19)F NMR spectroscopy in N[triple bond]SF(3) solvent (0 degrees C). Colorless [F(3)S(N[triple bond]SF(3))(2)][AsF(6)] crystallized from N[triple bond]SF(3) at -10 degrees C and was characterized by low-temperature, single-crystal X-ray diffraction. The S(IV) atom of F(3)S(N[triple bond]SF(3))(2)(+) has long contacts with the N atoms of two N[triple bond]SF(3) molecules and a F ligand of a neighboring AsF(6)(-) anion. The arrangement of long contacts avoids, to the maximum extent, the F atoms of SF(3)(+) and the nonbonding electron pair situated on the pseudo-3-fold axis opposite the F ligands of SF(3)(+), providing distorted octahedral coordination about the S(IV) atom. Quantum-chemical calculations using MP2, B3LYP, and PBE1PBE methods were employed to arrive at the gas-phase geometries, charges, bond orders, valencies, and vibrational frequencies for F(4)S=N-Xe---N[triple bond]SF(3)(+) and F(3)S(N[triple bond]SF(3))(2)(+) to aid in the assignments of experimental vibrational frequencies. The F(4)S=N-Xe---N[triple bond]SF(3)(+) cation expands the known chemistry of the F(4)S=N- group and is the first example of a N-Xe-N linkage to be structurally characterized by single-crystal X-ray diffraction.

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A fluorine magnetic resonance study of the solid addition compounds SF_4•AsF₅ and IF_7•AsF₅

Cited by 9 publications

References 2 publications

Ionic reorientations and phase transition in solid IF₆AsF₆

Ionic reorientations and phase transition in solid IF₆AsF₆

Spectroscopic study of IF7 and IF6+ in anhydrous hydrogen fluoride

On the Reactivity of F₃S≡NXeF⁺: Syntheses and Structural Characterizations of [F₄S═N−Xe---N≡SF₃][AsF₆], a Rare Example of a N−Xe−N Linkage, and [F₃S(N≡SF₃)₂][AsF₆]

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A fluorine magnetic resonance study of the solid addition compounds SF4•AsF5 and IF7•AsF5

Cited by 9 publications

References 2 publications

Ionic reorientations and phase transition in solid IF6AsF6

Ionic reorientations and phase transition in solid IF6AsF6

Spectroscopic study of IF7 and IF6+ in anhydrous hydrogen fluoride

On the Reactivity of F3S≡NXeF+: Syntheses and Structural Characterizations of [F4S═N−Xe---N≡SF3][AsF6], a Rare Example of a N−Xe−N Linkage, and [F3S(N≡SF3)2][AsF6]

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A fluorine magnetic resonance study of the solid addition compounds SF_4•AsF₅ and IF_7•AsF₅

Ionic reorientations and phase transition in solid IF₆AsF₆

Ionic reorientations and phase transition in solid IF₆AsF₆

On the Reactivity of F₃S≡NXeF⁺: Syntheses and Structural Characterizations of [F₄S═N−Xe---N≡SF₃][AsF₆], a Rare Example of a N−Xe−N Linkage, and [F₃S(N≡SF₃)₂][AsF₆]