フェロセン 化學特性,用途語,生産方法
外観
黃赤色?赤褐色, 結(jié)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，融點173～174 ℃，沸點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「化學辭典（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、醫(yī)薬等の合成中間體、觸媒、2.危険有害性の要約
構(gòu)造
二つの五員環(huán)の配置はねじれ形(図(a))とされたが，結(jié)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(huán)が約9°回転した配置をとっている．室溫で，ねじれ形構(gòu)造をとる証拠は得られていない．ガス狀態(tài)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體の[Fe{C5(CH3)5}2]はねじれ形である．Fe
2+ のかわりにほかの金屬イオンの入ったものを総稱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，F(xiàn)eCl2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．
特徴
164 K以上で単斜晶系，以下で三斜晶系と直方晶系，単斜晶系の場合結(jié)晶學的分子対稱Ci，近似的D5d対稱，Cpは互いにねじれ形，F(xiàn)e－C（平均）203.3 pm (293 K) (a)，203.3 pm (173 K) (a)(4)，C－C（平均） 138.9 pm (293 K)，139.5 pm (173 K)，三斜晶系の場合近似的D5対稱，Cpは互いに重なり形より約9?ずれている，F(xiàn)e－C（平均）204.1 pm (148 K) (b)，204.3 pm (123 K) (b)，20
化學的特性
Ferrocene, a metallocene, appears as bright orange salt-like crystals when crystallized from alcohol. It has a camphor-like odor and forms an orange crystalline solid. The compound is insoluble in water but soluble in benzene, ether, and alcohol, with an iron content of 29.4–30.6%.
物理的性質(zhì)
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(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).
調(diào)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.
主な応用
Ferrocene, the most well-known cyclopentadienyl sandwich compound, contains up to 30% iron. It is primarily used as an organometallic framework and is widely applied in fields such as aerospace, petroleum, chemical engineering and biomedicine. For example:
(1) Biomedicine: Research has revealed that ferrocene and its derivatives possess a wide range of pharmacological activities, such as anti-anaemic, antibacterial, anti-proliferative, anti-malarial, anti-tubercular and antiviral properties. Consequently, it can be utilised in the development of drug candidates for the treatment of iron-deficiency anaemia, cancer (e.g. tamoxifen, a drug used to treat hormone-dependent breast cancer) and malaria (e.g. chloroquine) [2].
(2) Aerospace sector: Among various catalysts for combustion rates, ferrocene and its derivatives demonstrate excellent catalytic performance. Currently, ferrocene-based catalysts for the oxidation of solid rocket propellants are in widespread use [3].
(3) Chemical Industry: Ferrocene is a well-known iron precursor molecule for depositing iron-containing films in processes such as chemical vapour deposition (CVD) and can be used to prepare iron nanoparticles. Ferrocene precursors are commonly used as suspension catalysts in the synthesis of carbon nanotubes (CNTs)[4]. Furthermore, it can serve as an iron source for the manufacture of low-cost catalyst supports used in fixed-bed CVD synthesis of carbon nanotubes.
(4) Petroleum sector: Ferrocene can be added to kerosene or diesel to enhance combustion efficiency and reduce carbon monoxide emissions, thereby achieving energy savings and reducing atmospheric pollution.
一般的な説明
Ferrocene appears as orange crystalline solid or orange-yellow powder. Sublimes above 212 °F. Camphor odor. (NTP, 1992)
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(zāi)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(yè)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 ℃.
參考文獻
(a) P. Seiler, J.D. Dunitz, Acta Crystallogr., Sect. B, 35, 1068 (1979), DOI: 10.1107/S0567740879005598；(b) P. Seiler, J.D. Dunitz, Acta Crystallogr., Sect. B, 35, 2020 (1979), DOI: 10.1107/S0567740879008384；(c) P. Seiler, J.D. Dunitz, Acta Crystallogr., Sect. B, 38, 1741 (1982), DOI: 10.1107/S0567740882007080.
フェロセン 上流と下流の製品情報
原材料
準備製品
[1,1'-ビス(ジ-tert-ブチルホスフィノ)フェロセン]パラジウム(II)ジクロリド
1,1'-フェロセンジカルボキシアルデヒド
1 1'-BIS(DIPHENYLPHOSPHINO)FERROCENE
1,1'-ビス(ジフェニルホスフィノ)フェロセン
1,1'-ジブチルフェロセン
1,1'-ビス(ジ-tert-ブチルホスフィノ)フェロセン
Ferrocene derivative
dibuty cebacate with ferric chloride
ブチルフェロセン
1,1'-ジメチルフェロセン
1,1'-ジアセチルフェロセン
1-ジフェニルホスフィノ-1'-(ジ-T-ブチルホスフィノ)フェロセン
1,1'-ビス(ジイソプロピルホスフィノ)フェロセン
Chlorocarbonyl ferrocene
1,1'-ジエチルフェロセン
メチルシクロペンタジエニルマンガントリカルボニル
ベンゾイルフェロセン
フェロセンボロン酸
1,1'-binaphthalene-2,2'-diyl diacetate
アセチルフェロセン
ferroceron