フェロセン

外観

黄赤色〜赤褐色, 結晶〜粉末

溶解性

エタノールにやや溶けにくく、水にほとんど溶けない。

解説

フェロセン，融点173～174 ℃，沸点249 ℃．密度1.49 g cm－3．普通の有機溶媒に可溶，水に不溶．100 ℃ 以上で昇華する．反磁性で，酸の共存下で空気酸化すると，青色のビス(η5-シクロペンタジエニル)鉄(Ⅲ)イオン [Fe(C5H5)2]＋ を生じる．ほかの芳香族化合物と同じく，求電子反応が起こりやすい．

森北出版「化学辞典（第2版）

用途

ガソリンのアンチノック剤、ロケット燃料の燃焼助剤、医薬等の合成中間体、触媒、2.危険有害性の要約

構造

二つの五員環の配置はねじれ形(図(a))とされたが，結晶中－175 ℃ では，重なり形(図(b))であり，－109 ℃ までは重なり形に近いが，上下の五員環が約9°回転した配置をとっている．室温で，ねじれ形構造をとる証拠は得られていない．ガス状態では重なり形をとる．理論的には重なり形が2.78 kJ mol－1 だけねじれ形より安定である．一方，多くのメタロセンはおもにねじれ形であり，またペンタメチル置換体の[Fe{C5(CH3)5}2]はねじれ形である．Fe²⁺ のかわりにほかの金属イオンの入ったものを総称してメタロセンという．

合成法

合成法には，無水塩化鉄FeCl3と臭化シクロペンタジエニルマグネシウムとの反応，FeCl2とシクロペンタジエニルナトリウムまたはシクロペンタジエニルリチウムとを反応させる方法，ジエチルアミンのような塩基の存在下にFeCl2とシクロペンタジエンとを反応させる方法などがある．

化学的特性

Ferrocene, a metallocene, is a bright orange salt-like crystals from alcohol. Camphor odor.

物理的性質

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.

使用

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.

定義

ferrocene: An orange-red crystallinesolid, Fe(C₅H₅)₂; m.p. 173°C. Itcan be made by adding the ioniccompound Na₊C₅H₅^- (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 theFe²⁺ ion. The compound can undergoelectrophilic substitution on theC₅H₅rings (they have some aromatic character).It can also be oxidized to theblue ion (C₅H₅)₂Fe⁺. Ferrocene is the first of a class of similar complexescalled sandwich compounds. Its systematicname is di-π-cyclopentadienyliron(II).

調製方法

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.

製造方法

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

一般的な説明

Orange crystalline solid or orange-yellow powder. Sublimes above 212°F. Camphor odor.

空気と水の反応

Sensitive to prolonged exposure to air and may be sensitive to light. Insoluble in water.

反応プロフィール

Ferrocene reacts violently with tetranitromethane. . Contact of tetranitromethane with Ferrocene under various conditions leads to violent explosion, [Trans. Met. Chem., 1979, 4, 207-208].

危険性

Moderate fire risk. Evolves toxic products on decomposition and heating.

健康ハザード

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.

火災危険

Flash point data for Ferrocene are not available. Ferrocene is probably combustible.

安全性プロファイル

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.

職業ばく露

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

発がん性

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.

輸送方法

UN1325 Flammable solids, organic, n.o.s., Hazard Class: 4.1; Labels: 4.1-Flammable solid.

純化方法

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.]

不和合性

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 ℃.