Selenium tetrafluoride
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
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- Selenium: Inorganic Chemistry Krebs. B., Bonmann S., Eidenschink I.; Encyclopedia of Inorganic Chemistry (1994) John Wiley and Sons Template:ISBN
See also
External links
Template:Selenium compounds Template:Fluorine compounds
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- ↑ 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. Script error: No such module "doi".
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