Oxidation of ruthenium and iridium metal by XeF2 and crystal structure determination of [Xe2F3][RuF6]∙XeF2 and [Xe2F3][MF6] (M = Ru, Ir)

Tramšek, Melita; Goreshnik, Evgeny; Tavčar, Gašper

doi:10.17344/acsi.2016.2373

Cited by 4 publications

(2 citation statements)

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“…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)]. 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)].…”

Section: Ngf 2 ·2crofmentioning

confidence: 59%

“…The bands at 465 (Kr) and 512 (Xe) cm À1 are assigned to the symmetric [n(Ng 1 ÀF 5 ) + n(Ng 1 ÀF 6 )] modes. 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)]. [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.…”

Section: Ngf 2 ·2crofmentioning

confidence: 96%

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

Mercier

Breddemann

Brock

et al. 2019

Chemistry A European J

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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.

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