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Selenium tetrafluoride

From Wikipedia, the free encyclopedia
Selenium tetrafluoride
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard100.033.352Edit this at Wikidata
UNII
  • InChI=1S/F4Se/c1-5(2,3)4 checkY
    Key: PMOBWAXBGUSOPS-UHFFFAOYSA-N checkY
  • InChI=1/F4Se/c1-5(2,3)4
    Key: PMOBWAXBGUSOPS-UHFFFAOYAQ
  • F[Se](F)(F)F
Properties
SeF4
Molar mass154.954 g/mol
Appearancecolourless liquid
Density2.77 g/cm3
Melting point−13.2 °C (8.2 °F; 259.9 K)
Boiling point101 °C (214 °F; 374 K)
Hazards
NFPA 704 (fire diamond)
Related compounds
Otheranions
selenium dioxide,selenium(IV) chloride,selenium(IV) bromide
Othercations
sulfur tetrafluoride,tellurium(IV) fluoride
Related compounds
selenium difluoride,selenium hexafluoride
Except where otherwise noted, data are given for materials in theirstandard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)
Chemical compound

Selenium tetrafluoride (SeF4) is aninorganic 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

[edit]

The first reported synthesis of selenium tetrafluoride was byPaul Lebeau in 1907, who treatedselenium withfluorine:[1]

Se + 2 F2 → SeF4

A synthesis involving more easily handled reagents entails the fluorination ofselenium dioxide withsulfur tetrafluoride:[2]

SF4 + SeO2 → SeF4 + SO2

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

Other methods of preparation include fluorinating elemental selenium withchlorine trifluoride:

3 Se + 4 ClF3 → 3 SeF4 + 2 Cl2

Structure and bonding

[edit]

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

[edit]

InHF, SeF4 behaves as a weak base, weaker thansulfur 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]Withcaesium fluoride, CsF, the SeF5 anion is formed, which has a square pyramidal structure similar to the isoelectronicchlorine pentafluoride, ClF5 andbromine 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

[edit]
  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 SonsISBN 0-471-93620-0

See also

[edit]

External links

[edit]
Selenium compounds
Se(−II)
Se(0,I)
Se(I)
Se(II)
Se(III)
Se(IV)
Se(VI)
Se(IV,VI)
Salts and covalent derivatives of thefluoride ion
HF?HeF2
LiFBeF2BF
BF3
B2F4
+BO3
CF4
CxFy
+CO3
NF3
FN3
N2F2
NF
N2F4
NF2
?NF5
+N
+NO3
OF2
O2F2
OF
O3F2
O4F2
?OF4
F2Ne
NaFMgF2AlF
AlF3
SiF4P2F4
PF3
PF5
+PO4
S2F2
SF2
S2F4
SF3
SF4
S2F10
SF6
+SO4
ClF
ClF3
ClF5
?ArF2
?ArF4
KFCaF
CaF2
ScF3TiF2
TiF3
TiF4
VF2
VF3
VF4
VF5
CrF2
CrF3
CrF4
CrF5
?CrF6
MnF2
MnF3
MnF4
?MnF5
FeF2
FeF3
FeF4
CoF2
CoF3
CoF4
NiF2
NiF3
NiF4
CuF
CuF2
?CuF3
ZnF2GaF2
GaF3
GeF2
GeF4
AsF3
AsF5
Se2F2
SeF4
SeF6
+SeO3
BrF
BrF3
BrF5
KrF2
?KrF4
?KrF6
RbFSrF
SrF2
YF3ZrF2
ZrF3
ZrF4
NbF4
NbF5
MoF4
MoF5
MoF6
TcF4
TcF
5

TcF6
RuF3
RuF
4

RuF5
RuF6
RhF3
RhF4
RhF5
RhF6
PdF2
Pd[PdF6]
PdF4
?PdF6
Ag2F
AgF
AgF2
AgF3
CdF2InF
InF3
SnF2
SnF4
SbF3
SbF5
TeF4
?Te2F10
TeF6
+TeO3
IF
IF3
IF5
IF7
+IO3
XeF2
XeF4
XeF6
?XeF8
CsFBaF2 LuF3HfF4TaF5WF4
WF5
WF6
ReF4
ReF5
ReF6
ReF7
OsF4
OsF5
OsF6
?OsF
7

?OsF
8
IrF2
IrF3
IrF4
IrF5
IrF6
PtF2
Pt[PtF6]
PtF4
PtF5
PtF6
AuF
AuF3
Au2F10
?AuF6
AuF5•F2
Hg2F2
HgF2
?HgF4
TlF
TlF3
PbF2
PbF4
BiF3
BiF5
PoF2
PoF4
PoF6
AtF
?AtF3
?AtF5
RnF2
?RnF
4

?RnF
6
FrFRaF2 LrF3RfDbSgBhHsMtDsRgCnNhFlMcLvTsOg
LaF3CeF3
CeF4
PrF3
PrF4
NdF2
NdF3
NdF4
PmF3SmF
SmF2
SmF3
EuF2
EuF3
GdF3TbF3
TbF4
DyF2
DyF3
DyF4
HoF3ErF3TmF2
TmF3
YbF2
YbF3
AcF3ThF2
ThF3
ThF4
PaF4
PaF5
UF3
UF4
UF5
UF6
NpF3
NpF4
NpF5
NpF6
PuF3
PuF4
PuF5
PuF6
AmF2
AmF3
AmF4
?AmF6
CmF3
CmF4
 ?CmF6
BkF3
BkF
4
CfF3
CfF4
EsF3
EsF4
?EsF6
FmMdF3No
PF6,AsF6,SbF6 compounds
AlF2−5,AlF3−6 compounds
chlorides, bromides, iodides
and pseudohalogenides
SiF2−6,GeF2−6 compounds
Oxyfluorides
Organofluorides
with transition metal,
lanthanide, actinide, ammonium
nitric acids
bifluorides
thionyl, phosphoryl,
and iodosyl
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