ChemInform Abstract: INFRARED SPECTRA OF METAL BISFLUOROSULFATES

Alleyne, Carl S.; Mailer, Kathleen O'sullivan; Thompson, Robert Clayton

doi:10.1002/chin.197416013

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“…The band separation between v4 and v,, the SO3 stretches, has decreased to about 110 + 10 cm-' from 206 cm-' in KS0,F (7) while v2, the SF stretch, has moved up by about 115 cm-' compared to its position in KS03F. This reflects a change in pn-d, back bonding on coordination through the three oxygen as has been noted before (2). The weighted average of the SO3 stretching bands in M(S03F), decreases from 1203 for Zn over 1198 to 1167 cm-' for Hg and may reflect the increase in the mass of the metal tightly held in the polymeric structure.…”

Section: Resultssupporting

confidence: 62%

“…l). Since all attempts so far have failed to obtain single crystals suitable for an X-ray diffraction study, and since the compounds are all high melting, d o not sublime, and are completely insoluble in HS03F and other inert solvents, evidence has come from infrared spectra (2), and in case of some transition metal fluorosulfates like Pd(S03F)2 (4), from their magnetic properties and the electronic spectra. Again a regular octahedral environment for Pd(I1) is indicated (4).…”

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Synthetic and Raman spectroscopic study of the fluorosulfates of zinc, cadmium, and mercury

Mallela¹,

Aubke²

1984

Can. J. Chem.

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Can. J . Chem. 62, 382 (1984). The group IIB metal fluorosulfates of the type M(SO,F),, with M = Zn, Cd, or Hg, are conveniently obtained in a simple one-step procedure: the metal oxidation in a mixture of bis(fluorosulfuryl)peroxide and fluorosulfuric acid. The resulting white polymeric solids are all excellent Raman scatterers and provide the first consistent set of Raman data for this structural type. Above 400 cm-' six sharp Raman lines indicate retention of C, , symmetry for the tridentate fluorosulfate groups, with coordination through oxygen evidenced by frequency shifts, in particular in the stretching range and the rigid polymeric structure causing a different band intensity pattern than the one found for ionic fluorosulfates. Bands below 300 cm-' are observed as well and some are tentatively assigned to skeletal metal-oxygen vibrations.S. P. MALLELA et F. AUBKE. Can. J. Chem. 62, 382 (1984). Utilisant un proctdC simple en une Ctape, ou a pu obtenir facilement des fluorosulfates des rnCtaux du groupe IIb du type M(S03F)2, ou M = Zn, Cd ou Hg: le procCdC implique une oxydation du mCtal dans un mklange de peroxyde de bis-(fluorosulfuryl) et d'acide fluorosulfurique. Les solides polymtriques blancs qui en resultent diffractent bien le Raman et permettent d'obtenir pour la premikre fois des donnCes cohCrentes en Raman pour ce type de structure. Au-dessus de 400 cm-', la presence de six lignes Raman bien dCfinies indique que la symCtrie C,, est retenue pour les groupes fluorosulfates tridentates, avec une coordination par le biais de l'oxygkne dCmontrCe par des dCplacements de frtquences, en particulier dans la rCgion de I'Clongation, et la structure polymCrique rigide provoquant un changement dans l'arrangement des intensitks des bandes par rapport B celui trouvC pour les fluorosulfates ioniques. On observe aussi la prCsence de bandes en-dessous de 300 cm-' et on en attribue quelques-unes des vibrations du squelette metal-oxygtne.[Traduit par le journal]

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confidence: 62%

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confidence: 99%