General Description
Orange crystalline solid or orange-yellow powder. Sublimes above 212°F. Camphor odor.
Reactivity Profile
FERROCENE(102-54-5) reacts violently with tetranitromethane. . Contact of tetranitromethane with FERROCENE(102-54-5) under various conditions leads to violent explosion, [Trans. Met. Chem., 1979, 4, 207-208].
Air & Water Reactions
Sensitive to prolonged exposure to air and may be sensitive to light. Insoluble in water.
Hazard
Moderate fire risk. Evolves toxic products
on decomposition and heating.
Potential Exposure
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
Fire Hazard
Flash point data for this chemical are not available. FERROCENE is probably combustible.
First aid
If this chemical gets into the eyes, remove any
contact lenses at once and irrigate immediately for at least
15 minutes, occasionally lifting upper and lower lids. Seek
medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately
with soap and water. Seek medical attention immediately.
If this chemical has been inhaled, remove from exposure,
begin rescue breathing (using universal precautions, includ ing resuscitation mask) if breathing has stopped and CPR if
heart action has stopped. Transfer promptly to a medical
facility. When this chemical has been swallowed, get medi cal attention. Give large quantities of water and induce
vomiting. Do not make an unconscious person vomit.
Shipping
UN1325 Flammable solids, organic, n.o.s.,
Hazard Class: 4.1; Labels: 4.1-Flammable solid.
Incompatibilities
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 ℃.
Description
Ferrocene, a metallocene, is a bright orangesalt-like crystals from alcohol with a camphor odor.Molecular weight = 186.05; Boiling point = 249 C (sublimes); Freezing/Melting point = 173 C. Decomposes at465 C. Hazard Identification (based on NFPA-704 MRating System): Health 2, Flammability 2, Reactivity 1.Insoluble in water.
Physical properties
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.
Preparation
Dicyclopentadienyliron may be obtained in a single-step synthetic route by heating cyclopentadiene with iron or iron pentacarbonyl at 300°C:
2C5H5 + Fe → (C5H5)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:
3C5H5MgBr + FeCl3 → (C5H5)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:
2C5H6 + 2Na → 2C5H5ˉ + 2Na+ + H2
In 3:2 molar ratio of cyclopentadiene to sodium cyclopentene is obtained along with cyclopentadienidide (C5H5ˉ ) anion:
3C5H6 + 2Na → 2C5H5¯ + 2Na+ + C5H8
FeCl2 + 2C5H6Na → (C5H5)2Fe + 2NaCl
Production Methods
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.
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.
Flammability and Explosibility
Highlyflammable
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.
storage
Color Code—Red: Flammability Hazard: Store ina flammable materials storage area. Prior to working withthis chemical you should be trained on its proper handlingand storage. Store in tightly closed containers in a cool,well-ventilated area away from oxidizers, ammonium perchlorate, tetranitromethane, mercury(II) nitrate, and heat.Sources of ignition, such as smoking and open flames, areprohibited where this chemical is used, handled, or stored ina manner that could create a potential fire or explosionhazard.
Purification Methods
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.]
Structure and conformation
X-ray diffraction studies show that in crystalline ferrocene (and in its
substituted derivatives) the iron atom is "sandwiched" between the two cyclopentadienyl
rings, these rings having the staggered configuration relative to each other (Fig. 16). The
rings are parallel plane regular pentagons, all the C-C and Fe-C distances being equal.
Electron diffraction studies show, however, that ferrocene has the eclipsed configuration
in the vapour state.
