Infrared and Raman Spectra of Krypton Difluoride

Claassen, Howard H.; Goodman, G. L.; Malm, John G.; Schreiner, F.

doi:10.1063/1.1696102

Cited by 51 publications

(25 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Theirf requencies are comparable to those of the Raman-active n 1 (S g + )m odes of free NgF 2 (Kr,4 65, [42] 469 [13] cm À1 ;X e, 515, [43] 496 [44] cm À1 )a nd are in accordance with the experimental NgÀFb ond length trends [NgF 2 ·2CrOF 4 :1 .8881(6) (Kr), 2.001(1) (Xe);f ree NgF 2 :1 .894(5) (Kr), 1.999(4) (Xe)].T he calculated frequencies and NgÀFb ond lengths follow the same trends [NgF 2 ·2CrOF 4 ;4 91 cm À1 ,1 .899 (Kr);5 34 cm À1 ,2 .023 (Xe); free NgF 2 :4 90 cm À1 ,1 .891 (Kr);5 05 cm À1 ,2 .012 (Xe)].T he symmetric stretching frequencies are also comparable to the in-phaseNgF 2 stretching frequencies of the bridging NgF 2 molecules in Hg(OTeF 5 ) 2 ·1.5NgF 2 [468 (Kr), 501 cm À1 (Xe)]. The bands assigned to theses tretches occur at 569 cm À1 (Kr) and5 53 cm À1 (Xe) and are similar to the infrared-active asymmetric stretching frequencies of free NgF 2 at 580/596cm À1 (Kr) [45] and 555 cm À1 (Xe) [43] .T he trend is reproduced by the calculated frequencies of NgF 2 ·2CrOF 4 [566 cm À1 (Kr), 562 cm À1 (Xe)] and free NgF 2 [582 cm À1 (Kr), 545 cm À1 (Xe)].A si nt he cases of NgF 2 ·CrOF 4 ,s ignificant vibrational mode coupling does not occur between the stretching modeso ft he NgF 2 and CrOF 4 groups. The bands assigned to theses tretches occur at 569 cm À1 (Kr) and5 53 cm À1 (Xe) and are similar to the infrared-active asymmetric stretching frequencies of free NgF 2 at 580/596cm À1 (Kr) [45] and 555 cm À1 (Xe) [43] .T he trend is reproduced by the calculated frequencies of NgF 2 ·2CrOF 4 [566 cm À1 (Kr), 562 cm À1 (Xe)] and free NgF 2 [582 cm À1 (Kr), 545 cm À1 (Xe)].A si nt he cases of NgF 2 ·CrOF 4 ,s ignificant vibrational mode coupling does not occur between the stretching modeso ft he NgF 2 and CrOF 4 groups.…”

Section: Ngf 2 ·2crofsupporting

confidence: 58%

“…[37] The NgF 2 ligands, which lie in s-planes, are asymmetric which renders their [n(Ng 1 ÀF 5 )-n(Ng 1 ÀF 6 )] modesb oth Ramanand infrared-active. The bands assigned to theses tretches occur at 569 cm À1 (Kr) and5 53 cm À1 (Xe) and are similar to the infrared-active asymmetric stretching frequencies of free NgF 2 at 580/596cm À1 (Kr) [45] and 555 cm À1 (Xe) [43] .T he trend is reproduced by the calculated frequencies of NgF 2 ·2CrOF 4 [566 cm À1 (Kr), 562 cm À1 (Xe)] and free NgF 2 [582 cm À1 (Kr), 545 cm À1 (Xe)].A si nt he cases of NgF 2 ·CrOF 4 ,s ignificant vibrational mode coupling does not occur between the stretching modeso ft he NgF 2 and CrOF 4 groups. The d(F t NgF b ) i.p.…”

Section: Ngf 2 ·2crofmentioning

confidence: 57%

See 1 more Smart Citation

Syntheses, Structures, and Bonding of NgF₂⋅CrOF₄, NgF₂⋅2CrOF₄(Ng=Kr, Xe), and (CrOF₄)_∞

Mercier

Breddemann

Brock

et al. 2019

Chemistry A European J

View full text Add to dashboard Cite

The noble‐gas difluoride adducts, NgF2⋅CrOF4 and NgF2⋅2CrOF4 (Ng=Kr and Xe), have been synthesized and structurally characterized at low temperatures by Raman spectroscopy and single‐crystal X‐ray diffraction. The low fluoride ion affinity of CrOF4 renders it incapable of inducing fluoride ion transfer from NgF2 (Ng=Kr and Xe) to form ion‐paired salts of the [NgF]+ cations having either the [CrOF5]− or [Cr2O2F9]− anions. The crystal structures show the NgF2⋅CrOF4 adducts are comprised of Ft−Ng−Fb‐ ‐ ‐Cr(O)F4 structural units in which NgF2 is weakly coordinated to CrOF4 by means of a fluorine bridge, Fb, in which Ng−Fb is elongated relative to the terminal Ng−Ft bond. In contrast with XeF2⋅2MOF4 (M=Mo or W) and KrF2⋅2MoOF4, in which the Lewis acidic, F4(O)M‐ ‐ ‐Fb‐ ‐ ‐M(O)F3 moiety coordinates to Ng through a single M‐ ‐ ‐Fb−Ng bridge, both fluorine ligands of NgF2 coordinate to CrOF4 molecules to form F4(O)Cr‐ ‐ ‐Fb−Ng−Fb‐ ‐ ‐Cr(O)F4 adducts in which both Ng−Fb bonds are only marginally elongated relative to the Ng−F bonds of free NgF2. Quantum‐chemical calculations show that the Cr−Fb bonds of NgF2⋅CrOF4 and NgF2⋅2CrOF4 are predominantly electrostatic with a small degree of covalent character that accounts for their nonlinear Cr‐ ‐ ‐Fb−Ng bridge angles and staggered O−Cr‐ ‐ ‐Fb−Ng−Ft dihedral angles. The crystal structures and Raman spectra of two CrOF4 polymorphs have also been obtained. Both are comprised of fluorine‐bridged chains that are cis‐ and trans‐fluorine‐bridged with respect to oxygen.

show abstract

Section: Ngf 2 ·2crofsupporting

confidence: 58%

Section: Ngf 2 ·2crofmentioning

confidence: 57%

Syntheses, Structures, and Bonding of NgF₂⋅CrOF₄, NgF₂⋅2CrOF₄(Ng=Kr, Xe), and (CrOF₄)_∞

Mercier

Breddemann

Brock

et al. 2019

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…As explained in [I], the y-value for the Kr, F pair lies in the range 1.6-2.0. Experimental evidence [7] indicates further that the R,-value in KrF, is close to that in XeF,; the reported distance of 1.9 f 0.1 A has not been determined directly, but inferred from infrared and Raman spectra. With These results show that KrF, is in any case less stable than XeF, (y-effect).…”

Section: Numerical Results and Discussionmentioning

confidence: 80%

Validity of the three‐center, four‐electron model for stability of rare gas halides on the basis of exchange perturbation theory

Lombardi

Pirola

Tarantini

et al. 1974

Int J of Quantum Chemistry

View full text Add to dashboard Cite

AbstractsIn a previous publication [l] we analyzed the stability of rare gas halides on the basis of exchange perturbation theory of the Rayleigh-Schrodinger type, using a three-center, four-electron model. In this paper, the analysis is extended to a (n + 1)-center, (n + 2)-electron model for rare gas halides of composition RX, , where R is the rare gas atom and X the halogen atom, in order to investigate the validity of the three-center, fourelectron model. The compounds analyzed are XeF, , XeCl, , KrF, and KrCl, with n = 3 and 4, in different geometric configurations and for different states of total spin S.As before, we use exchange perturbation theory in first and second orders. The results are in good agreement with those obtained in the previous analysis and with experiments. Specifically, it is found that chlorides of rare gas atoms are not stable, that XeF4 has the square-planar configuration and that trifluorides cannot exist. The possible existence of KrF, is discussed.Dam une publication rtcente [l], nous avons analyst la stabilitt des halogtnures des gaz rares sur la base d'une thtorie de perturbation du type de Rayleigh-Schrodinger gknkraliste pour les forces d'tchange, en utilisant un modtle A quatre tlectrons sur trois centres. Dans cet article, l'analyse est gtntraliste A un systtme de (n + 2)-tlectrons sur (n + 1)-centres, ceci pour ttudier les halogtnures des gaz rares de composition RX, , oh R est l'atome des gaz rares et X l'halogtne, et pour ttablir la validitt du modkle de quatre tlectrons sur trois centres. Les composts analysts sont XeF, , XeCl, , KrF, et KrCl, , avec n = 3 et n = 4, pour difftrentes configurations gtomttriques et pour difftrents ttats de spin total S. Comme auparavant, nous utilisons la thtorie de perturbation du type d'tchange en premier et deuxitme ordres. Les rksultats sont en bon accord avec ceux obtenus dans l'analyse prtctdente et avec l'exptrience. En particulier, on trouve que les chlorures des gaz rares ne sont pas stables, que XeFp a la configuration de forme plan-carrke et que les tri-fluorures ne peuvent pas exister. L'existence possible de KrF4 est discutte.I n einer kiirzlich erschienenen Arbeit [l] wurde das Problem der Stabilitat der Edelgashalogenide auf der Basis eines "drei-Zentren, vier-E1ektronen"-Modells unter Verwendung von Austausch-S torungsrechnung vom Typ Rayleigh-Schr8dinger analysiert. 335

show abstract

“…The coupled Kr−F b stretching modes are assigned to overlapping bands between 449 and 508 cm −1 (calcd; 413–467 cm −1 (B3LYP), 438–492 cm −1 (APFD)), which are also similar to those of Mg(KrF 2 ) 4 (AsF 6 ) 2 (449/460, 467/475, 486, 495 cm −1 ), F 2 OBr(KrF 2 ) 2 (AsF 6 ) (443, 472 cm −1 ), and the Raman‐active symmetric stretching mode (ν 1 ,

Σ \binom{+}{g}

) of solid KrF 2 at 466.5 cm −1 . The F−Kr−F bending modes are assigned to bands at 238, 262, and 282 cm −1 (calcd; 219–255 cm −1 (B3LYP), 231–286 cm −1 (APFD)) and are also in accordance with those of Mg(KrF 2 ) 4 (AsF 6 ) 2 (227, 293 cm −1 ), F 2 OBr(KrF 2 ) 2 (AsF 6 ) (254, 266, 301 cm −1 ), and the doubly degenerate IR‐active bending mode of gas‐phase KrF 2 (232.6 cm −1 ) …”

Section: Figurementioning

confidence: 88%

A Homoleptic KrF₂ Complex, [Hg(KrF₂)₈][AsF₆]₂⋅2 HF

DeBackere

Schrobilgen

2018

Angewandte Chemie

View full text Add to dashboard Cite

The reaction of Hg(AsF6)2 with a large molar excess of KrF2 in anhydrous HF has afforded the first homoleptic KrF2 coordination complex of a metal cation, [Hg(KrF2)8][AsF6]2⋅2 HF. The [Hg(KrF2)8]2+ dication is well‐isolated in the low‐temperature crystal structure of its HF‐solvated [AsF6]− salt, and consists of eight KrF2 molecules that are terminally coordinated to Hg2+ by means of Hg−F(KrF) bonds to form a slightly distorted, square‐antiprismatic coordination sphere around mercury. The Raman spectrum of [Hg(KrF2)8]2+ was assigned with the aid of calculated gas‐phase vibrational frequencies. Computational studies indicate that both electrostatic and orbital interactions are important for metal–ligand bonding and provide insight into the geometry of the [Hg(KrF2)8]2+ cation and the nature of noble‐gas difluoride ligand bonding.

show abstract

Infrared and Raman Spectra of Krypton Difluoride

Cited by 51 publications

References 9 publications

Syntheses, Structures, and Bonding of NgF₂⋅CrOF₄, NgF₂⋅2CrOF₄(Ng=Kr, Xe), and (CrOF₄)_∞

Syntheses, Structures, and Bonding of NgF₂⋅CrOF₄, NgF₂⋅2CrOF₄(Ng=Kr, Xe), and (CrOF₄)_∞

Validity of the three‐center, four‐electron model for stability of rare gas halides on the basis of exchange perturbation theory

A Homoleptic KrF₂ Complex, [Hg(KrF₂)₈][AsF₆]₂⋅2 HF

Contact Info

Product

Resources

About

Infrared and Raman Spectra of Krypton Difluoride

Cited by 51 publications

References 9 publications

Syntheses, Structures, and Bonding of NgF2⋅CrOF4, NgF2⋅2CrOF4(Ng=Kr, Xe), and (CrOF4)∞

Syntheses, Structures, and Bonding of NgF2⋅CrOF4, NgF2⋅2CrOF4(Ng=Kr, Xe), and (CrOF4)∞

Validity of the three‐center, four‐electron model for stability of rare gas halides on the basis of exchange perturbation theory

A Homoleptic KrF2 Complex, [Hg(KrF2)8][AsF6]2⋅2 HF

Contact Info

Product

Resources

About

Syntheses, Structures, and Bonding of NgF₂⋅CrOF₄, NgF₂⋅2CrOF₄(Ng=Kr, Xe), and (CrOF₄)_∞

Syntheses, Structures, and Bonding of NgF₂⋅CrOF₄, NgF₂⋅2CrOF₄(Ng=Kr, Xe), and (CrOF₄)_∞

A Homoleptic KrF₂ Complex, [Hg(KrF₂)₈][AsF₆]₂⋅2 HF