Ferrocen Chemische Eigenschaften,Einsatz,Produktion Methoden
ERSCHEINUNGSBILD
ORANGEFARBENE KRISTALLE MIT CHARAKTERISTISCHEM GERUCH.
CHEMISCHE GEFAHREN
Beim Verbrennen Bildung von giftigen Rauchen. Reagiert sehr heftig mit Ammoniumperchlorat oder Tetranitromethan. Reagiert mit Quecksilber(II)nitrat.
ARBEITSPLATZGRENZWERTE
TLV: (als Eisen) 10 mg/m?(als TWA); (ACGIH 2005).
MAK nicht festgelegt (DFG 2005).
AUFNAHMEWEGE
Aufnahme in den Körper durch Inhalation und durch Verschlucken.
INHALATIONSGEFAHREN
Verdampfung bei 20°C vernachlässigbar; eine gesundheitsschädliche Partikelkonzentration in der Luft kann jedoch beim Dispergieren schnell erreicht werden.
WIRKUNGEN BEI KURZZEITEXPOSITION
WIRKUNGEN BEI KURZZEITEXPOSITION: Reizt möglicherweise mechanisch.
LECKAGE
Verschüttetes Material in Behältern sammeln; falls erforderlich durch Anfeuchten Staubentwicklung verhindern. Persönliche Schutzausrüstung: Atemschutzgerät, P1-Filter für inerte Partikel.
R-Sätze Betriebsanweisung:
R11:Leichtentzündlich.
R22:Gesundheitsschädlich beim Verschlucken.
R51/53:Giftig für Wasserorganismen, kann in Gewässern längerfristig schädliche Wirkungen haben.
S-Sätze Betriebsanweisung:
S61:Freisetzung in die Umwelt vermeiden. Besondere Anweisungen einholen/Sicherheitsdatenblatt zu Rate ziehen.
S22:Staub nicht einatmen.
Chemische Eigenschaften
Ferrocene, a metallocene, is a bright orange
salt-like crystals from alcohol. Camphor odor.
Physikalische Eigenschaften
Orange crystals; camphor-like odor; melts at 172.5°C; vaporizes at 249°C; sublimes above 100°C; thermally stable above 500°C; insoluble in water; soluble in alcohol, ether and benzene; also soluble in dilute nitric acid and concentrated sulfuric acid forming a deep red solution that fluoresces.
Verwenden
Ferrocene
is used as a catalyst for vulcanization, acceleration, and
polymerization, as a chemical intermediate for polymeric
compounds such as high temperature polymers, as an antiknock
additive for gasoline, as a coating for missiles and
satellites, and as a high-temperature lubricant.
Definition
ferrocene: An orange-red crystallinesolid, Fe(C
5H
5)
2; m.p. 173°C. Itcan be made by adding the ioniccompound Na
+C
5H
5- (cyclopentadienylsodium, made from sodium andcyclopentadiene) to iron(III) chloride.In ferrocene, the two rings are parallel,with the iron ion sandwiched betweenthem (hence the namesandwich compound: see formula).The bonding is between pi orbitalson the rings and d-orbitals on theFe
2+ ion. The compound can undergoelectrophilic substitution on theC
5H
5rings (they have some aromatic character).It can also be oxidized to theblue ion (C
5H
5)
2Fe
+. Ferrocene is the first of a class of similar complexescalled sandwich compounds. Its systematicname is di-π-cyclopentadienyliron(II).
Vorbereitung Methode
Ferrocene is produced from the reaction of cyclopentadiene
with reduced iron in the presence of metal oxides. There is
also a two-stage production process in which produced iron
(II)oxide (stage 1) is reacted with cyclopentadiene.
synthetische
Dicyclopentadienyliron may be obtained in a single-step synthetic route by heating cyclopentadiene with iron or iron pentacarbonyl at 300°C:
2C
5H
5 + Fe → (C
5H
5)
2Fe
Also, it can be prepared by the reaction of iron(II) chloride with cyclopentadiene in the presence of an alkyl amine or a similar base.
Another convenient method of preparing this π-complex of iron is a twostep process in which the first step involves preparation of cyclopentadienyl Grignard reagent, such as 2,4-cyclopentadienylmagnesium bromide C5H5MgBr which may then be combined with ferric chloride to yield dicyclopentadienyl iron:
3C
5H
5MgBr + FeCl
3 → (C
5H
5)
2Fe + 3MgBrCl
Another general method of preparation involves the reaction of cyclopentadiene with sodium metal or sodium hydride in tetrahydrofuran (THF). Addition of iron(II) chloride to this solution forms the complex dicyclopentadienyliron:
2C
5H
6 + 2Na → 2C
5H
5ˉ + 2Na+ + H
2
In 3:2 molar ratio of cyclopentadiene to sodium cyclopentene is obtained along with cyclopentadienidide (C
5H
5ˉ ) anion:
3C
5H
6 + 2Na → 2C5H5¯ + 2Na+ + C
5H
8
FeCl
2 + 2C5H
6Na → (C5H5)
2Fe + 2NaCl
Allgemeine Beschreibung
Orange crystalline solid or orange-yellow powder. Sublimes above 212°F. Camphor odor.
Air & Water Reaktionen
Sensitive to prolonged exposure to air and may be sensitive to light. Insoluble in water.
Reaktivität anzeigen
Ferrocene reacts violently with tetranitromethane. . Contact of tetranitromethane with Ferrocene under various conditions leads to violent explosion, [Trans. Met. Chem., 1979, 4, 207-208].
Hazard
Moderate fire risk. Evolves toxic products
on decomposition and heating.
Health Hazard
Dicyclopentadienyl iron causes
changes in blood parameters and hepatic
cirrhosis.
The toxicological properties of dicyclopentadienyl
iron have not been extensively
investigated. However, it has been used as a
preventive and therapeutic iron deficiency
drug, and its utilization is listed as tolerable.
Brandgefahr
Flash point data for Ferrocene are not available. Ferrocene is probably combustible.
Sicherheitsprofil
Poison by
intraperitoneal and intravenous routes.
Moderately toxic by ingestion. Questionable
carcinogen with experimental tumorigenic
data. Mutation data reported. Flammable;
reacts violently with NH4ClO4. When heated
to decomposition it emits acrid smoke and
irritating fumes.
mögliche Exposition
Used as additive in fuel oil; antiknock
agent in gasoline fuel; used in making rubber, silicone
resins, high-temperature polymers and lubricants; interme diate for high-temperature polymers; as a smoke suppres sant and catalyst
Carcinogenicity
Ferrocene was administered by
intramuscular injection at a dose of 5175 mg/kg/2 years.
By the criterion established by the Registry of Toxic Effects
of Chemical Substances (RTECS), ferrocene was an equivocal
tumorigenic agent and tumors were most evident at the
site of multiple injections.
Versand/Shipping
UN1325 Flammable solids, organic, n.o.s.,
Hazard Class: 4.1; Labels: 4.1-Flammable solid.
läuterung methode
Purify it by crystallisation from pentane or cyclohexane (also *C6H6 or MeOH can be used). It is moderately soluble in Et2O and sublimes readily above 100o. Crystallisation from EtOH gave material m 172.5-173o. [Wilkinson Org Synth Coll Vol IV 473 1963, Miller J Chem Soc 632 1952.] It has also been crystallised from methanol and sublimed in vacuo. [Saltiel et al. J Am Chem Soc 109 1209 1987, Beilstein 16 IV 1783.]
Inkompatibilitäten
Violent reaction with ammonium per chlorate, tetranitromethane, mercury(II) nitrate. Incompa tible with oxidizers (chlorates, nitrates, peroxides, perman ganates, perchlorates, chlorine, bromine, fluorine, etc.);
contact may cause fires or explosions. Keep away from
alkaline materials, strong bases, strong acids, oxoacids,
epoxides.
Peroxomonosulfuric acid. Decomposes @≧465 ℃.
Ferrocen Upstream-Materialien And Downstream Produkte
Upstream-Materialien
Downstream Produkte
1,1'-Bis (di-t-butylphosphino)ferrocene palladium dichloride,
1,1'-FERROCENEDICARBOXALDEHYDE
1 1'-BIS(DIPHENYLPHOSPHINO)FERROCENE
1,1'-Bis(diphenylphosphino)ferrocene
1,1'-Dibutylferrocen
1,1'-Bis(di-tert-butylphosphino)ferrocene
Ferrocene derivative
dibuty cebacate with ferric chloride
Butylferrocen
1,1'-Dimethylferrocen
1,1'-Diacetylferrocene
1-DIPHENYLPHOSPHINO-1'-(DI-TERT-BUTYLPH&
1,1'-BIS(DIISOPROPYLPHOSPHINO)FERROCENE
Chlorocarbonyl ferrocene
1,1'-DIETHYLFERROCENE
Tricarbonyl-(methylcyclopentadie-nyl)-mangan
Benzoylferrocen
Ferrocenmetaborsure
1,1'-binaphthalene-2,2'-diyl diacetate
Acetylferrocen
