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by | Mar 21, 2018 | Euonymus

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Selenium tetrafluoride (SeF4) is an inorganic compound. It is a colourless liquid that reacts readily with water. It can be used as a fluorinating reagent in organic syntheses (fluorination of alcohols, carboxylic acids or carbonyl compounds) and has advantages over sulfur tetrafluoride in that milder conditions can be employed and it is a liquid rather than a gas.

Synthesis

The first reported synthesis of selenium tetrafluoride was by Paul Lebeau in 1907, who treated selenium with fluorine:[1]

Se + 2 F2 → SeF4

A synthesis involving more easily handled reagents entails the fluorination of selenium dioxide with sulfur tetrafluoride:[2]

SF4 + SeO2 → SeF4 + SO2

An intermediate in this reaction is seleninyl fluoride (SeOF2).

Other methods of preparation include fluorinating elemental selenium with chlorine trifluoride:

3 Se + 4 ClF3 → 3 SeF4 + 2 Cl2

Structure and bonding

Selenium in SeF4 has an oxidation state of +4. Its shape in the gaseous phase is similar to that of SF4, having a see-saw shape. VSEPR theory predicts a pseudo-trigonal pyramidal disposition of the five electron pairs around the selenium atom. The axial Se-F bonds are 177 pm with an F-Se-F bond angle of 169.2°. The two other fluorine atoms are attached by shorter bonds (168 pm), with an F-Se-F bond angle of 100.6°. In solution at low concentrations this monomeric structure predominates, but at higher concentrations evidence suggests weak association between SeF4 molecules leading to a distorted octahedral coordination around the selenium atom. In the solid the selenium center also has a distorted octahedral environment.

Reactions

In HF, SeF4 behaves as a weak base, weaker than sulfur tetrafluoride, SF4 (Kb= 2 X 10−2):

SeF4 + HF → SeF3+ + HF2−; (Kb = 4 X 10−4)

Ionic adducts containing the SeF3+ cation are formed with SbF5, AsF5, NbF5, TaF5, and BF3.[3] With caesium fluoride, CsF, the SeF5− anion is formed, which has a square pyramidal structure similar to the isoelectronic chlorine pentafluoride, ClF5 and bromine pentafluoride, BrF5.[4] With 1,1,3,3,5,5-hexamethylpiperidinium fluoride or 1,2-dimethylpropyltrimethylammonium fluoride, the SeF62− anion is formed. This has a distorted octahedral shape which contrasts to the regular octahedral shape of the analogous SeCl62−. [5]

References

  1. ^ Paul Lebeau (1907). "Action of Fluorine on Selenium Tetrafluoride of Selenium". Comptes Rendus de l'Académie des Sciences de Paris. 144: 1042.
  2. ^ Konrad Seppelt, Dieter Lentz, Gerhard Klöter "Selenium Tetrafluoride, Selenium Difluoride Oxide (Seleninyl Fluoride), and Xenon Bis[Pentafluorooxoselenate(VI)]" Inorg. Synth., 1987, vol. 24, 27-31. doi:10.1002/9780470132555.ch9
  3. ^ R. J. Gillespie; A. Whitla (1970). "Selenium tetrafluoride adducts. II. Adducts with boron trifluoride and some pentafluorides". Can. J. Chem. 48 (4): 657–663. doi:10.1139/v70-106.
  4. ^ K. O. Christe; E. C. Curtis; C. J. Schack; D. Pilipovich (1972). "Vibrational Spectra and Force Constants of the Square-Pyramidal Anions SF5−, SeF5−, and TeF5−". Inorganic Chemistry. 11 (7): 1679–1682. doi:10.1021/ic50113a046.
  5. ^ Ali Reza Mahjoub; Xiongzhi Zhang; Konrad Seppelt (1995). "Reactions of the Naked Fluoride Ion: Syntheses and Structures of SeF62− and BrF6−". Chemistry: A European Journal. 1 (4): 261–265. doi:10.1002/chem.19950010410.
  • Selenium: Inorganic Chemistry Krebs. B., Bonmann S., Eidenschink I.; Encyclopedia of Inorganic Chemistry (1994) John Wiley and Sons ISBN 0-471-93620-0

See also

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