102-54-5

Basic information

• Product Name: Ferrocene
• Synonyms: BIS(CYCLOPENTADIEN)IRON;BIS(CYCLOPENTADIENYL)IRON;BIS(CYCLOPENTADIENYL)IRON(+2);FERROCENE;IRON DICYCLOPENTADIENYL;di-2,4-cyclopentadien-1-yliron;DICYCLOPENTADIENYLIRON;DICYCLOPENTADIENYLIRON(II)
• CAS NO: 102-54-5
• Molecular Formula: C₁₀H₁₀Fe
• Molecular Weight: 186.03
• EINECS: 203-039-3
• Product Categories: Organometallics;Classes of Metal Compounds;Fe (Iron) Compounds;Ferrocenes;Metallocenes;Transition Metal Compounds;metallocene
• Mol File: 102-54-5.mol
• Article Data: 224

Chemical Properties

• Melting Point: 172-174 °C(lit.)
• Boiling Point: 249 °C(lit.)
• Flash Point: 100°C
• Appearance: orange/crystal
• Density: 1.490
• Vapor Pressure: 0.03 mm Hg ( 40 °C)
• Storage Temp.: Flammables area
• Water Solubility: practically insoluble
• Sensitive: Air & Moisture Sensitive
• Stability: Stable at room temperature. Incompatible with strong oxidizing agents. Highly flammable.
• Merck: 14,4037
• CAS DataBase Reference: Ferrocene(CAS DataBase Reference)
• NIST Chemistry Reference: Ferrocene(102-54-5)
• EPA Substance Registry System: Ferrocene(102-54-5)

Safety Data

• Hazard Codes: F,Xn,N
• Statements: 11-22-51/53-2017/11/22
• Safety Statements: 61-22-24/25
• RIDADR: UN 1325 4.1/PG 2
• WGK Germany: 2
• RTECS: LK0700000
• TSCA: Yes
• HazardClass: 4.1
• PackingGroup: II
• Hazardous Substances Data: 102-54-5(Hazardous Substances Data)

Usage

Chemical Description

Ferrocene is an organometallic compound consisting of two cyclopentadienyl rings bound to an iron atom.

A kind of organic transition metal compound with aromatic property

Ferrocene is a kind of organic transition metal compound with aromatic nature. It is also called as dicyclopentadienyl iron. It contains a divalent iron cation and two cyclopentadienyl anions in its molecular structure. It is also the raw materials for production of ferrocenecarboxylic acid. In 1950s of the last century, people had first successfully produced it with the reaction between cyclopentadienyl magnesium bromide and anhydrous ferric chloride. At room temperature, it is orange needle crystal powder with a similar smell as camphor and belongs to non-polar compound. It is soluble in many organic solvents such as methanol, ethanol, ethyl ether, petroleum ether, gasoline, kerosene, diesel oil, methylene chloride, benzene, toluene, and xylene, Because of the large polarity of ethanol polarity, it is usually recommended to dissolve it with toluene. It is insoluble in water but soluble in concentrated sulfuric acid. It is also insoluble and doesn’t decompose in boiling caustic soda solution and hydrochloric acid. It molecule exhibits polarity with higher thermal stability, chemical stability and radiation resistance. It has wide range of application in industry, agriculture, medicine, aerospace, energy, environmental protection and other industries. Main applications are described below: (1)It can be used as the fuel saving smoke suppressants and anti-knock agent. For example, it can be used for the production of gasoline antiknock agent, the fuel catalyst of rocket propellant and also the solid fuels of aerospace. (2) It can be used as the catalyst such as catalyst for the production of ammonia, as the curing agent of silicone rubber; it can prevent the degradation of polyethylene by light; when applied to agricultural mulch, it can break its natural degradation without affecting the cultivation and fertilization within a certain time. (3) It can be used as a gasoline anti-knock agent. It can substitute gasoline toxic tetraethyl lead for being used as the anti-knock agent and for production of high-grade unleaded petrol in order to eliminate the contamination of the environment and poisoning to human body by discharge of fuel. (4) It can be used as radiation absorbers, heat stabilizers, light stabilizers, and smoke-retardants. (5) For the chemical properties, ferrocene is similar to aromatic compounds which is not prone to have addition reaction but prone to have electrophilic substitution reaction. It can also participate in metallization, acylation, alkylation, sulfonation, formylation and ligand exchange reaction, which can be used for production of derivative with a wide range of applications. The above information is edited by the lookchem of Dai Xiongfeng.

Chemical Properties

Different sources of media describe the Chemical Properties of 102-54-5 differently. You can refer to the following data:
1. It is an orange needles like crystal with its melting point being 172.5-173 ℃. It undergoes sublimation at temperature higher than 100 ℃. Its boiling point is 249 ℃. It is soluble in dilute nitric acid, concentrated sulfuric acid, benzene, ether, petroleum ether and tetrahydrofuran. It can generate bluish fluorescence-containing deep red solution in dilute nitric acid and concentrated sulfuric acid. It is insoluble in water, 10% sodium hydroxide and hot concentrated hydrochloric acid. In the boiling solution of these solvents, ferrocene is neither dissolved nor decomposed. It can be evaporated together with water vapor. It has a smell similar to camphor and is stable in air. It has a strong property of UV absorbing and has great thermostability which can withstand the heating at a temperature as high as 470 ℃.
2. Orange, crystalline solid; camphor-like odor. Insoluble in water; soluble in benzene, ether, and alcohol. Iron content 29.4–30.6%.
3. Ferrocene, a metallocene, is a bright orange salt-like crystals from alcohol. Camphor odor.

Uses

Different sources of media describe the Uses of 102-54-5 differently. You can refer to the following data:
1. Ferrocene can be used as the additives of rocket fuel, the antiknock agent of gasoline and the curing agent of rubber and silicone resin as well as the ultraviolet absorber. The Vinyl derivative of ferrocene can be subject to ethylenic polymerization to obtain the metal-containing polymers of carbon chain skeleton which can be used as the outer coating of spacecraft. It has been found early regarding the smoke abatement effect and combustion effect of ferrocene. No matter whether being supplied in solid fuel, liquid fuel or gas fuel, it can always exert this kind of effect and this effect is more significant especially for hydrocarbons with smoke upon burning. Supplement it into the gasoline has a very good anti-hunt effect. However, due to the deposition of the iron oxide in park plug which can negatively affect ignition, its application is limited, therefore, some people also apply de-iron mixture in order to reduce the deposition phenomenon of iron. Supplement of ferrocene to the kerosene or diesel oil, due to the absence of ignition device in the engine, will have fewer adverse effects on it. In addition to the smoke abatement and combustion facilitating effect in the combustion, it also has effect of promoting the conversion of carbon monoxide into carbon dioxide. In addition, it can improve the heat of combustion and increase power efficiency to achieve the effects of energy saving and air pollution reduction. Supplement of ferrocene to the boiler fuel oil can reduce tobacco production and nozzle deposition. Supplement of 0.1% ferrocene in diesel can remove smoke by 30-70%, save fuel by 10-14%, and increase the power by 10%. There are even many more reports regarding the application of ferrocene in solid fuel of rocket fuel. Moreover, there are even cases regarding supplying it in pulverized coal for smoke-reduction agent. Upon applying the polymer water as fuel, supplement of ferrocene can reduce the smoke by several times. It can also be used as the smoke-reducing additive. In addition to the above applications, ferrocene also has other applications. When used as iron fertilizer, it can facilitate the absorption of plants on iron and increase the iron content of crops. Moreover, its derivatives can be used as pesticides. Ferrocene also has a lot of applications in industry and organic synthesis. For example, its derivatives can be used as the antioxidant of rubber or polyethylene, the stabilizer of polyurea ester, the catalyst of isobutene spasm methylation, the decomposition catalyst of polymer peroxide, and for increasing the yield of para-chlorotoluene produced during the process of chlorination of toluene. In other areas, it can also be used as anti-load additive of lubricants as well as the promoting agent of abrasive materials. It can be used as catalyst and the antiknock additive of gasoline as well as energy-saving additives for combustion promotion and smoke removal; it can be applied to various kinds of fuels such as diesel, gasoline, heavy oil and coal. Supplement of 0.1% ferrocene into diesel can save fuel by 10-14%, increase the efficiency by 10-13%, and reduce the degree of smoke in exhaust by 30-80 ‰. In addition, addition of 0.3 ‰ to the heavy oil and addition of 0.2% ferrocene to coal can both decrease the fuel consumption rate while the degree of smoke is also reduced by 30%. Ferrocene is a kind of sandwich-containing metal compound. Ferrocene and its derivatives, because of their own characteristics such as hydrophobicity, bio-oxidability, aroma, stability, low resistance, biological activity, has a wide range of application such as catalyst, the antiknock additive of gasoline, high-temperature lubricant, the intermediates of high-temperature polymer and UV absorber.
2. 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.
3. In ultraviolet stabilizers and smoke depressants for polymers; to increase the burn rate of rocket propellants; to prevent erosion of space capsule shields; to improve the viscosity of lubricants; to catalyze polymerization reactions; to catalyze combustion; some derivatives used as hematinic agents
4. Antiknock additive for gasoline; catalyst.

Production method

It can be produced either by the heating reaction between iron powder and cyclopentadiene in nitrogen atmosphere of 300 ℃ or the reaction between anhydrous ferric chloride together with the sodium cyclopentadienyl in tetrahydrofuran. Alternatively, it can also produced by electrolytic synthesis method. Taking cyclopentadiene, ferrous chloride, and diethylamine as raw material for synthesis of ferrocene can operate according to the following protocol. Upon stirring, add anhydrous ferric chloride (FeCl3) in several times to the tetrahydrofuran solution; further add iron powder into it and have heating reflux for 4.5 h under the protection of nitrogen gas, resulting in ferrous chloride solution. Further remove tetrahydrofuran solvent by evaporation under reduced pressure to give nearly dry residue. Under ice-cooling condition, add the mixture of cyclopentadienyl and diethylamine and stir vigorously at room temperature for 6-8h; remove the excess amount of amine through evaporation under reduced pressure and extract the residue with petroleum ether under reflux. The extract is subject to immediate filtering; evaporate the solvent to obtain ferrocene crude product. Employ pentane or cyclohexane for recrystallization, or apply sublimation method for extract purified product with the yield of refined product being 73-84%.

Category

toxic substances

Toxicity grading

poisoning

Acute toxicity

Oral-rat LD50: 1320 mg/kg; Oral-Mouse LD50: 832 mg/kg.

Flammability and hazard characteristics

flammable with the combustion generating iron-containing acrid smoke

Storage properties

warehouse: ventilated, low temperature and dry; Store it separately from oxidants.

Extinguishing agent

Water, carbon dioxide, dry, sandy soil.

Professional standards

TWA 10 mg/m3; STEL 20 mg/m3

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.

Definition

Different sources of media describe the Definition of 102-54-5 differently. You can refer to the following data:
1. A coordination compound of ferrous iron and two molecules of cyclopentadiene in which the organic portions have typically aromatic chemical properties. Its activity is intermediate between phenol and anisole. The first compound shown to have the “sandwich
2. An orange crystalline solid. It is an example of a sandwich compound, in which an iron(II) ion is coordinated to two cyclopentadienyl ions. The bonding involves overlap of d orbitals on the iron with the pi electrons in the cyclopentadienyl ring. The compound melts at 173°C, is soluble in organic solvents, and can undergo substitution reactions on the rings. It can be oxidized to the blue cation (C5H5)2Fe+. The systematic name is di-π-cyclopentadienyl iron(II).
3. 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).

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.

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 → 2C5H5ˉ + 2Na+ + C5H8 FeCl2 + 2C5H6Na → (C5H5)2Fe + 2NaCl

General Description

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

Air & Water Reactions

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

Reactivity Profile

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.

Fire Hazard

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

Flammability and Explosibility

Highlyflammable

Safety Profile

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.

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

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.

Shipping

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

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.

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 ℃.

InChI:InChI=1/2C5H5.Fe/c2*1-2-4-5-3-1;/h2*1-3H,4H2;/rC10H10Fe/c1-2-6-9(5-1)11-10-7-3-4-8-10/h1-5,7H,6,8H2

Synthetic route

ferrocenyl(triphenylphosphine)gold → ferrocene (102-54-5)

Conditions	Yield
With potassium cyanide In chloroform; water byproducts: P(C6H5)3; (Ar); shaking a soln. of the Au complex in CHCl3 with aq. KCN, 8 h; sepn. of the org. layer, drying over K2CO3, evapn. to dryness; products determined by thin-layer chromy. and 1H-NMR;	100%
In not given with electrophilic reacgents;;

ferrocenium(III) tetrafluoroborate (1282-37-7) + dicarbonyl(η5-cyclopentadienyl)(η1-7-methoxy-1-cycloheptenyl)iron (95865-41-1) → ferrocene (102-54-5) + dicarbonyl(η5-cyclopentadienyl)(η1-7-methoxycycloheptene-1-carbonyl)iron (95865-47-7)

Conditions	Yield
With `CO In dichloromethane Addn. of Cp2FeBF4 to iron-compd. (methylene chloride, 55 psiCO, 1h).; Removal of solvent (vacuo), elution with hexane (alumina column) gives yellow band of ferrocene, elution with CH2Cl2 gives yellow band of dicarbonyl complex, elem. anal.;	A n/a B 99%

ferrocenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (156301-37-0) + ([3,5-(2,4,6-i-Pr3C6H2)2C6H3NCH2CH2]3N)Mo(η2-C2H2) → ferrocene (102-54-5) + [([3,5-(2,4,6-i-Pr3C6H2)2C6H3NCH2CH2]3N)Mo(C2H2)][B(3,5-(CF3)2C6H3)4]

Conditions	Yield
In benzene under N2 atm. to soln. Mo complex in benzene (Cp2Fe)(BAr'4) was added and stirred for 30 min; volatiles were removed in vacuo, residue was dissolved in heptane, ppt. was dried in high vac.; elem. anal.;	A n/a B 99%

ferrocenium trifluoromethanesulfonate + tris-(o-tolyl)phosphine (6163-58-2) → ferrocene (102-54-5) + tri(o-tolyl)phosphonium trifluoromethanesulfonate salt

Conditions	Yield
With C26H46ClO3Ru2S2(1+)*CF3O3S(1-); hydrogen In dichloromethane at 20℃; under 760.051 Torr; for 11h; Catalytic behavior; Inert atmosphere;	A 99% B 98%

cyclopenta-1,3-diene (542-92-7) + iron(II) bromide → ferrocene (102-54-5)

Conditions	Yield
With iron; diethylamine In further solvent(s) further solvents: mixt. of HN(C2H5)2, CH3OH, DME and (C6H5CH2N(CH3)3)OH; amine method; FeBr2 and Fe from Fe and Br2, Fe excess;;	98%
With diethylamine In 1,2-dimethoxyethane; diethylamine amine method; FeBr2 from Fe and Br2;;	85%
With diethylamine In 1,2-dimethoxyethane; diethylamine amine method; FeBr2 from Fe and Br2;;	85%
With diethylamine In diethylamine byproducts: HBr;	4%

ferrocenium hexafluorophosphate + tetra-n-butylammonium tetramethylaurate(III) → ferrocene (102-54-5) + gold (7440-57-5, 457905-15-6)

Conditions	Yield
In acetonitrile byproducts: CH4, C2H6; inert atmosphere;	A 92% B 98%
In tetrahydrofuran byproducts: CH4, C2H6; inert atmosphere;	A 94% B 95%

ferrocenium hexafluorophosphate + tetra-n-butylammonium tetramethylaurate(III) + triphenylphosphine (603-35-0) → ferrocene (102-54-5) + trimethyl(triphenylphosphine)gold(III)

Conditions	Yield
In tetrahydrofuran byproducts: CH4; He-atmosphere; -196°C, addn. of Cp2FePF6 to soln. of aurate and PPh3; not sepd., NMR-spectroscopy;	A 98% B 98%
In diethyl ether byproducts: CH4, C2H6; inert atmosphere;	A 95% B 94%
In acetonitrile byproducts: CH4; inert atmosphere; -40°C;	A 94% B 89%

1,2-bis((η6-4-chlorophenoxy-η5-cyclopentadienyl)iron)benzene hexafluorophosphate → ferrocene (102-54-5) + 1,2-bis-(4-chlorophenoxy)benzene (153288-01-8)

Conditions	Yield
In dichloromethane; acetonitrile Irradiation (UV/VIS); addn. of diiron-complex dissolved in CH2Cl2/CH3CN to a photolysis tube, purging with N2 for 30 min, irradiation under intense visible light (Xenon lamp) for 4 h; concn. by evapn. under reduced pressure, column chromy., elution (hexane) gives yellow band of ferrocene, elution (hexane/CHCl3) gives benzene-compd., evapn. to dryness, elem. anal.;	A n/a B 98%

[C6H5S(O)CH2](1-)*Li(1+)=[C6H5S(O)CH2]Li (59501-96-1) + (C5H5)Fe[P(OC6H5)3]2Cl (84430-52-4) → ferrocene (102-54-5) + bis(phenylthio)methane (3561-67-9) + 1,2-bis(phenylthio)ethane (622-20-8) + diphenyldisulfane (882-33-7) + lithium chloride

Conditions	Yield
In tetrahydrofuran mixing reactants in THF at -78°C, slow warming to room temp. / further products; evapn. in vac., extn. with pentane, ether and finally acetone or CH2Cl2, concn., chromy. on Al2O3, purifn. by crystn., distn. or sublimation;	A 27% B 27% C 38% D 25% E 98%

ferrocenium hexafluorophosphate + tetrabutylammonium dimethylaurate(I) (228118-52-3) → ferrocene (102-54-5) + gold (7440-57-5, 457905-15-6)

Conditions	Yield
In tetrahydrofuran byproducts: CH4, C2H6; He-atmosphere; addn. of 1 equiv. of Cp2FePF6 to soln. of aurate at -196°C, warming to room temp.;	A 94% B 97%
In acetonitrile byproducts: CH4, C2H6; He-atmosphere; addn. of 1 equiv. of Cp2FePF6 to soln. of aurate at -196°C, warming to room temp.;	A 96% B 96%

[(η6-p-xylene)(η5-cyclopentadienyl)iron(II)](hexafluorophosphate) + acetonitrile (75-05-8) → ferrocene (102-54-5)

Conditions	Yield
In acetonitrile byproducts: Fe(II), p-xylene; Irradiation (UV/VIS); a CH3CN soln. of Fe-compd. was degassed by bubbling with N2 for 10 min and irradiated with sunlight for 3 h 25 min at room temp.;; evapn. of the solvent and extn. the residue with cyclohexane; detected by NMR-expt.;;	97%
In acetonitrile byproducts: Fe(II), p-xylene; Irradiation (UV/VIS); a CH3CN soln. of Fe-compd. was degassed by bubbling with N2 for 10 min and irradiated with an Oriel lamp for 3 h 25 min at room temp.;; evapn. of the solvent and extn. the residue with cyclohexane; detected by NMR-expt.;;	93%

ferrocenium tetrakis(pentafluorophenyl)borate (135348-57-1) + Ti(N[tBu](3,5-Me2C6H3))3 → ferrocene (102-54-5) + [Ti(N[tBu](3,5-Me2C6H3))3][B(C6F5)4]

Conditions	Yield
In diethyl ether for 0.5h; Inert atmosphere; Schlenk technique; Glovebox;	A 80% B 97%

cyclopentadienylthallium (34822-90-7) + iron(III) chloride (7705-08-0) → ferrocene (102-54-5)

Conditions	Yield
In tetrahydrofuran anhyd. FeCl3, boiling abs. THF, under exclusion of air; preparation of small amts.;;	96%

lithiumferrocene (1271-15-4) + lead(II) chloride → lead (7439-92-1) + ferrocene (102-54-5)

Conditions	Yield
In diethyl ether byproducts: LiCl; Ar; to a suspn. of PbCl2 added a suspn. of FcLi, stirred for 2 h; ppt. (Pb) filtered, washed (H2O), dried, analyzed; Fc not isolated, detected by NMR;	A 96% B n/a

4,4'-bis((η6-phenoxy-η5-cyclopentadienyl)iron)biphenyl hexafluorophosphate → ferrocene (102-54-5) + 4,4'-diphenoxy-1,1'-biphenyl (2519-16-6)

Conditions	Yield
In dichloromethane; acetonitrile Irradiation (UV/VIS); addn. of diiron-complex dissolved in CH2Cl2/CH3CN to a photolysis tube, purging with N2 for 30 min, irradiation under intense visible light (Xenon lamp) for 4 h; concn. by evapn. under reduced pressure, column chromy., elution (hexane) gives yellow band of ferrocene, elution (hexane/CHCl3) gives benzene-compd., evapn. to dryness, elem. anal.;	A n/a B 96%

1,2-bis((η6-4-methylphenoxy-η5-cyclopentadienyl)iron)benzene hexafluorophosphate → ferrocene (102-54-5) + 1,2-bis-(4-methylphenoxy)benzene (153287-98-0)

Conditions	Yield
In dichloromethane; acetonitrile Irradiation (UV/VIS); addn. of diiron-complex dissolved in CH2Cl2/CH3CN to a photolysis tube, purging with N2 for 30 min, irradiation under intense visible light (Xenon lamp) for 4 h; concn. by evapn. under reduced pressure, column chromy., elution (hexane) gives yellow band of ferrocene, elution (hexane/CHCl3) gives benzene-compd., evapn. to dryness, elem. anal.;	A n/a B 96%

ferrocenium(III) tetrafluoroborate (1282-37-7) + (triphenylphosphane)gold(I) tert-butylthiolate (122711-31-3) → ferrocene (102-54-5) + tetrakis(triphenylphosphane)bis(tert-butylthiolate)tetragold(I) tetrafluoroborate

Conditions	Yield
In dichloromethane byproducts: (SC(CH3)3)2; N2, Fe:Au=0.136:0.276 molar ratio, Fe compd. added to a soln. of Au compd., stirred for 30 min; solvent evapd., residue washed (diethyl ether, benzene), dried (vac.), recrystd. (CH2Cl2, -5°C), org. phases evapd. to dryness, ferrocenesublimied (40°C, high vac.); elem. anal.;	A n/a B 96%

ferrocenium hexafluorophosphate + C6H3(C(CH2CH2CH2Si(CH3)2CH2OC6H4C(CH2CH2CH2Si(CH3)2CH2N3C2HC5H4FeC5H4C5H4FeC5H5)3)3)3 → ferrocene (102-54-5) + C6H3(C(CH2CH2CH2Si(CH3)2CH2OC6H4C(CH2CH2CH2Si(CH3)2CH2N3C2HC5H4FeC5H4C5H4FeC5H5)3)3)3(27+)*27PF6(1-)

Conditions	Yield
In dichloromethane byproducts: ferrocene; 27 equivs. of (C5H5)Fe(C5H5)(PF6) in CH2Cl2 added to dendrimer complex in CH2Cl2 at room temp.; allowed to stir under N2 for 1 h at room temp.; Et2O added dropwise; filtered under N2 on Celite; dried in vac.; elem. anal.;	A 96% B 66.3%

{fc-P(C6H5)2CH2C6H5}OH → ferrocene (102-54-5) + (diphenylphosphinoyl)ferrocene + fc-PO(C6H5)(CH2C6H5) + toluene (108-88-3) + benzene (71-43-2)

Conditions	Yield
With potassium chloride In 1,2-dimethoxyethane; water ratio H2O:(CH2OCH3)2 = 50:50 %, 0.4 M KCl, boiling; not isolated;	A n/a B 35.9% C n/a D 95.3% E 3.9%
With KCl In 1,2-dimethoxyethane; water ratio H2O:(CH2OCH3)2 = 50:50 %, 0.4 M KCl, boiling; not isolated;	A n/a B 35.9% C n/a D 95.3% E 3.9%

ferrocenium hexafluorophosphate + di(t-butylimido)di(2,4,6-trimethylphenyl)rhenium(VI) (126572-58-5) → ferrocene (102-54-5) + di(t-butylimido)di(2,4,6-trimethylphenyl)rhenium(VII) hexafluorophosphate

Conditions	Yield
In tetrahydrofuran absence of air; stirring (1 h); solvent removal (vac.), washing (hexane), crystn. (THF/Et2O); elem. anal.;	A n/a B 95%

1,2-bis((η6-phenoxy-η5-cyclopentadienyl)iron)benzene hexafluorophosphate → ferrocene (102-54-5) + 1,2-diphenoxybenzene (3379-37-1)

Conditions	Yield
In dichloromethane; acetonitrile Irradiation (UV/VIS); addn. of diiron-complex dissolved in CH2Cl2/CH3CN to a photolysis tube, purging with N2 for 30 min, irradiation under intense visible light (Xenon lamp) for 4 h; concn. (vac.), column chromy., elution (hexane) gives yellow band of ferrocene, elution (hexane/CHCl3) gives benzene-compd., evapn. to dryness, elem. anal.;	A n/a B 95%

ferrocenium(III) tetrafluoroborate (1282-37-7) + bis[(1,2-bis(dimethylphosphino)ethane)(η(5)-methylcyclopentadienyl)manganese(I)](μ-2,3-diphenylbutadien-1,4-diylidene) (223424-75-7) → ferrocene (102-54-5) + bis[(1,2-bis(dimethylphopshino)ethane)(η(5)-methylcyclopentadienyl)manganese(III)](μ-2,3-diphenylbut-2-en-1,4-diylidyne) bis(tetrafluoroborate)

Conditions	Yield
In dichloromethane N2-atmosphere; filtering, concg., pptn. on Et2O addn.; collecting, washing (Et2O), drying (vac.), repptn., recrystn. (CH2Cl2, room temp.); elem. anal.;	A n/a B 95%

(η(5)-2-cyclopentadienyl-2-indenyl-propane)Rh(1,5-cyclooctadiene) (209473-49-4) + [(cyclopentadienyl)Fe(fluorene)]PF6 (232282-91-6) → ferrocene (102-54-5) + [Rh(cyclooctadiene)(η5-cyclopentadienyl)C(CH3)2(η5-indenyl)Fe(η5-cyclopentadienyl)] (329985-01-5, 912572-47-5)

Conditions	Yield
With BuLi In tetrahydrofuran byproducts: fluorene; (N2); (COD)Rh(Cp)C(CH3)2(C9H6) deprotonated with BuLi in THF; soln. prepared from (CpFe(fluorene))PF6 and BuLi added at 0 °C after 1 h; refluxed for 16 h; solvend removed; extracted by pentane/diethyl ether (1:1); chromy.(pentane/diethyl ether); elem. anal.;	A n/a B 95%

ferrocenium(III) tetrafluoroborate (1282-37-7) + (methyldiphenylphosphane)gold(I) tetr-butylthiolate (1002113-69-0) → ferrocene (102-54-5) + tetrakis(methyldiphenylphosphane)bis(tert-butylthiolate)tetragold(I) tetrafluoroborate

Conditions	Yield
In dichloromethane byproducts: (SC(CH3)3)2; N2, Fe:Au=0.136:0.276 molar ratio, Fe compd. added to a soln. of Au compd., stirred for 30 min; solvent evapd., residue washed (diethyl ether, benzene), dried (vac.), recrystd. (CH2Cl2, -5°C), org. phases evapd. to dryness, ferrocenesublimied (40°C, high vac.); elem. anal.;	A n/a B 95%

ferrocenium hexafluorophosphate + W6S8(P(C2H5)3)6 → ferrocene (102-54-5) + W6S8(P(C2H5)3)6(1+)*PF6(1-)=W6S8(P(C2H5)3)6PF6

Conditions	Yield
In benzene W-cluster was dissolved in benzene in Schlenk flask, soln. of Fe-complexwas added, stirred for 1 h; after 2 d filtered, washed with Et2O, dried;	A n/a B 95%
In dichloromethane W-cluster was dissolved in CH2Cl2 in Schlenk flask, soln. of Fe-complex in CH2Cl2 was added, stirred for 30 min; solvent was removed under vac. washed with benzene and Et2O;	A n/a B 85%

1,1'-dibromoferrocene (1293-65-8) + water (7732-18-5) → ferrocene (102-54-5) + bromoferrocene (1273-73-0)

Conditions	Yield
With n-butyllithium In tetrahydrofuran under N2; n-BuLi in THF added dropwise at -35°C to soln. of Fe complex in THF; stirred at -35°C for 1 h; H2O added dropwise; warmed to room temp. over 1 h; extd. with Et2O; org. layer collected; washed with H2O; dried (Na2SO4); solvent removed under reduced pressure; bromoferrocene contaminated withferrocene (10%);	A n/a B 95%

ferrocenium trifluoromethanesulfonate → ferrocene (102-54-5) + trifluorormethanesulfonic acid (1493-13-6)

Conditions	Yield
With C26H46ClO3Ru2S2(1+)*CF3O3S(1-); hydrogen In water at 20℃; under 760.051 Torr; for 1.2h; Catalytic behavior; Temperature; Reagent/catalyst; Inert atmosphere; Schlenk technique;	A 95% B n/a
With [(pentamethylcyclopentadienyl)Ru{PhP(C6H4-o-S)2}Ru(pentamethylcyclopentadienyl)](OTf)2; hydrogen In water at 20℃; under 760.051 Torr; for 20h;	A 87% B 86%
With [η5-C5Me5Ru(μ-SiPr)2Ru(OH2)-η5-C5Me5](OTf)2; hydrogen In methanol at 20℃; under 760.051 Torr; for 1.4h; Temperature; Reagent/catalyst; Solvent; Pressure; Schlenk technique;

ferrocenium hexafluorophosphate → ferrocene (102-54-5)

Conditions	Yield
With tetramethylpiperidine; H2; Cp*Ru(dppf)H In acetone (Ar);; concn., extn. (hexanes);	94%
With 1,7-dilithio-m-carborane In cyclohexane byproducts: LiPF6, m-carborane; (N2 or Ar); heated at 80°C for 24 h; quenched with wet n-hexane, passed through silica gel, washed (ether), the org. portions combined, evapd. (vac.), flash-chromd. (silica gel, n-hexane);	49%
With sodium benzotriazolide In tetrahydrofuran at 20°C;

ferrocenium(III) tetrafluoroborate (1282-37-7) + Cp2Ta{(μ-CH2)2}CoCp → ferrocene (102-54-5) + {Cp2Ta(μ-CH2)2Co(CH3CN)Cp}(1+)BF4(1-)*CH3CN

Conditions	Yield
In acetonitrile 20 °C; variable temp. NMR;	A n/a B 94%

1,3-bis((η6-phenoxy-η5-cyclopentadienyl)iron)benzene hexafluorophosphate → ferrocene (102-54-5) + 1,3-diphenoxybenzene (3379-38-2)

Conditions	Yield
In dichloromethane; acetonitrile Irradiation (UV/VIS); addn. of diiron-complex dissolved in CH2Cl2/CH3CN to a photolysis tube, purging with N2 for 30 min, irradiation under intense visible light (Xenon lamp) for 4 h; concn. by evapn. under reduced pressure, column chromy., elution (hexane) gives yellow band of ferrocene, elution (hexane/CHCl3) gives benzene-compd., evapn. to dryness, elem. anal.;	A n/a B 94%

ferrocene (102-54-5) + phenyl isocyanate (103-71-9) → N-phenylferrocenecarboxamide

Conditions	Yield
With trifluorormethanesulfonic acid at 25℃; for 8h; Reagent/catalyst; Temperature; Inert atmosphere;	100%
With aluminium trichloride	25%
With AlCl3	25%
aluminium trichloride In carbon disulfide

ferrocene (102-54-5) → ferricinium chloroferrate

Conditions	Yield
With hydrogenchloride; oxygen; iron(III) chloride In diethyl ether passing O2 through mixt. of ferrocene in ether and FeCl3 in aq. HCl;;	100%
With FeCl3; O2; HCl In diethyl ether passing O2 through mixt. of ferrocene in ether and FeCl3 in aq. HCl;;	100%
With sulfuryl dichloride In benzene in boiling benzene, equimolar amt. of ferrocene and SO2Cl2;;	97%

ferrocene (102-54-5) + β-cyclodextrin decahydrate → ferrocene, β-cyclodextrin complex

Conditions	Yield
In water molar ratio cyclodextrin : ferrocene = 1:4, addn. of crystals of ferrocene to an aq. soln. of cyclodextrin at 60°C with stirring; washed with water, dried in vac., washed with THF, recrystn. from water or aq. alcohol; elem. anal.;	100%
In ethanol; water molar ratio cyclodextrin : ferrocene = 2:1, an aq. alcohol soln. of cyclodextrin (40% ethanol) was mixed with an aq. alcohol soln. of ferrocene (60% ethanol); addn. of water and/or partial removal of ethanol by evapn.; elem. anal.;	85%
In ethanol; water molar ratio cyclodextrin : ferrocene = 1:1, addn. of aq. soln. of cyclodextrin to an alcohol soln. of ferrocene with stirring and heating; elem. anal.;	56%
In ethanol; water molar ratio cyclodextrin : ferrocene = 1:1, addn. of aq. soln. of cyclodextrin to an alcohol soln. of ferrocene with stirring and heating; elem. anal.;	36%

ferrocene (102-54-5) + [Cu((NCH2CH2)3(CH(CH3)2)2(CH2C6H2(O)(C(CH3)3)2))OSO2CF3](1+) → ferrocenium (12125-80-3) + [Cu((NCH2CH2)3(CH(CH3)2)2(CH2C6H2(O)(C(CH3)3)2))OSO2CF3]

Conditions	Yield
In not given stoichiometric amt.;	A n/a B 100%

ferrocene (102-54-5) + 2-ferrocenyl-6-methyl-pyridin-4-yl nonaflate → 2-methyl-4,6-bisferrocenyl pyridine (152602-97-6)

Conditions	Yield
Stage #1: ferrocene With potassium tert-butylate In tetrahydrofuran Inert atmosphere; Schlenk technique; Stage #2: With tert.-butyl lithium In tetrahydrofuran; pentane at -30℃; for 1h; Inert atmosphere; Stage #3: 2-ferrocenyl-6-methyl-pyridin-4-yl nonaflate Further stages;	100%

ferrocene (102-54-5) + 3-diazonium-o-carborane tetrafluoroborate → C12H20B10Fe

Conditions	Yield
With eosin In acetonitrile at 20℃; for 2h; Inert atmosphere; Schlenk technique; Irradiation; regioselective reaction;	100%

ferrocene (102-54-5) + hydrogen fluoride (7664-39-3) + phosphorus pentafluoride (7647-19-0, 874483-74-6) → C10H11Fe(1+)*F6P(1-)

Conditions	Yield
at -196 - 20℃; Sealed tube;	100%

ferrocene (102-54-5) + 2-methylimidazole (693-98-1) → [iron(II)(2-methylimidazolate)2]

Conditions	Yield
With 4,4'-bipyridine at 150℃; for 48h; Reagent/catalyst;	100%

ferrocene (102-54-5) + perfluoro-o-phenylenemercury trimer (18734-63-9) → 2(HgC6F4)3*Fe(C5H5)2

Conditions	Yield
In dichloromethane soln. of (HgC6F5)3 (0.096 mol) in CH2Cl2 mixed with soln. ferrocene (0.538 mol) in CH2Cl2; crystd. by slow evapn. of solvent; crystals washed (hexane); elem. anal.;	99%
In dichloromethane no react. in CH2Cl2 soln.; (199)Hg NMR;	0%

hexafluorophosphoric acid + ferrocene (102-54-5) + pentamethylbenzene, (700-12-9) → {(Cp)iron(II)(η6-pentamethylbenzene)}(PF6) (112596-54-0)

Conditions	Yield
With aluminium trichloride; aluminium In neat (no solvent) ferrocene, Al-powder and AlCl3 are ground in a mortar, the arene is added and mixt. is reground, rapidly transferred to a microwave app. (react. time 3 min) and heated; complex is isolated by adding water and pptg. with HPF6 from the aq. soln.;	99%
With aluminium trichloride; water; aluminium In not given treatment of ferrocene with benzene deriv. in presence of aluminium, AlCl3 and 1 equiv. of water at 100°C; Hamon J.R., Astruc D., MichaudP., J. Am. Chem. Soc., 1981, 103, 758-766; treatment with aq. ammonia, treatment with HPF6;

ferricenium tetrakis(pentafluorophenyl)borate (135348-57-1) + Ti(N[tBu](3,5-Me2C6H3))3 → ferrocene (102-54-5) + [Ti(N[tBu](3,5-Me2C6H3))3][B(C6F5)4]

Conditions	Yield
In diethyl ether for 0.5h; Inert atmosphere; Schlenk technique; Glovebox;	A 80% B 97%

ferrocene (102-54-5) + benzaldehyde (100-52-7) → Ferrocenyl(phenyl)carbenium perchlorate

Conditions	Yield
With trichlorophosphate In perchloric acid; diethyl ether aq. HClO4 addn. to ferrocene, carbonyl compd. and POCl3 (room temp., over 2 h), addn. of ether, standing (15 h), pptn.; collection (filtration), washing (ether); elem. anal.;	99%

ferrocene (102-54-5) + benzoyl chloride (98-88-4) → 1,1’-dibenzoylferrocene (12180-80-2, 32983-90-7)

Conditions	Yield
With aluminium chloride In dichloromethane ferrocene (1.0 equiv.) added to a stirred suspension of benzoyl chloride(2.2 equiv.) and aluminium chloride (2.2 equiv.) in dichloromethane, st irred at room temp. overnight (16 h); washed with water, organic layer passed through a plug of alumina, washed with chloroform, washings concentrated in vacuo, crude product purified by flash column chromy. on silica gel (TLC Rf 0.26 (1:1 ether-hexane)), elem. anal.;	99%
With aluminium trichloride In dichloromethane to suspn. of AlCl3 in CH2Cl2 ligand was added, soln. of Fe-complex in CH2Cl2 was added, stirred for 3 ds at room temp. under Ar; aq. soln. of NaHCO3 was added, extd. with CH2Cl2, washed with aq. NaHCO3, dried over MgSO4, concd. under reduced pressure, column chromy. on silica gel with pentane-Et2O; elem. anal.;	87%
With aluminium trichloride; benzoyl chloride In dichloromethane soln. of C6H5COCl and AlCl3 in dry CH2Cl2 was added dropwise over a period of 1 h to a stirred soln. of ferrocene in dry CH2Cl2; soln. was refluxed for 30 min, hydrolized with 0.1 M HCl, product worked up; solid chromd. on alumina using benzene, following by ether ewluant;	86%
With aluminum (III) chloride In dichloromethane at 0℃; for 0.5h; Inert atmosphere; Schlenk technique;	75%
With AlCl3 In dichloromethane

Indole-3-carboxaldehyde (487-89-8) + ferrocene (102-54-5) → (C5H5FeC5H4CHC8H5NH)(1+)*ClO4(1-)=(C5H5FeC5H4CHC8H5NH)ClO4

Conditions	Yield
With trichlorophosphate In perchloric acid; diethyl ether aq. HClO4 addn. to ferrocene, carbonyl compd. and POCl3 (room temp., over 1 h), addn. of ether, standing (15 h), pptn.; collection (filtration), washing (ether); elem. anal.;	99%

ammonium hexafluorophosphate + ferrocene (102-54-5) + <33>(1,3,5)-cyclophane (13821-31-3) → bis(η(5)-cyclopentadienyl)(η(6),η(6)-[3(3)](1,3,5)cyclophane)diiron(II,II) bis(hexafluorophosphate)

Conditions	Yield
With aluminium trichloride; aluminium In decalin Ar-atmosphere; heating cyclophane with excess of Fe-complex, AlCl3 and Al (160°C, 2 h), cooling in ice bath, washing aq. layer (Et2O), filtration, addn. of excess of aq. NH4PF6 (pptn.); filtration, drying (vac., room temp.); elem. anal.;	99%

ferrocene (102-54-5) + Co(C27H34N4O4) → (C5H5)2Fe(1+)*Co(C27H34N4O4)(1-)=[(C5H5)2Fe][Co(C27H34N4O4)] (212846-49-6)

Conditions	Yield
In cyclohexane excess Cp2Fe (pptn.); centrifugation;	99%

ferrocene (102-54-5) + Co(C27H32Cl2N4O4) → (C5H5)2Fe(1+)*Co(C27H32Cl2N4O4)(1-)=[(C5H5)2Fe][Co(C27H32Cl2N4O4)] (212846-59-8)

Conditions	Yield
In cyclohexane excess Cp2Fe (pptn.); centrifugation;	99%

ferrocene (102-54-5) + [Fe(η5-cyclopentadienyl)(η-benzene)] → (η-C5H5)Fe(μ-η:η-C5H5)Fe(η-C5H5)

Conditions	Yield
In dichloromethane Irradiation (UV/VIS); irradiation (visible light, 250 W luminescence lamp), 0°C, 1 h, intense stirring; soln. concentrating in vacuum, residue washing repeatedly by petroleum ether, vacuum drying; elem. anal.;	99%

ferrocene (102-54-5) + mercury(II) trichloroacetate (15873-63-9, 20464-21-5) + sodium chloride (7647-14-5) → decakis(chloridomercury(II))ferrocene

Conditions	Yield
In methanol; diethyl ether; water addn. of soln. of ferocene (in Et2O) to soln. of Hg-salt (in MeOH), stirring (ambient temp., 15 - 30 min), pouring into ice H2O, satd. with NaCl, stirring (2 h); filtration, washing, (15 % aq. KI, satd. aq. NaCl, H2O, EtOH and ether),drying; elem. anal.;	99%
In methanol; water 50°C; addn. of soln. of ferocene (in Et2O) to soln. of Hg-salt (in MeOH), stirring (ambient temp., 15 - 30 min), pouring into ice H2O, satd. with NaCl, stirring (2 h); filtration, washing, (15 % aq. KI, satd. aq. NaCl, H2O, EtOH and ether),drying; elem. anal.;	99%
In methanol; water addn. of ferocene to soln. of Hg-salt (in MeOH), stirring (ambient temp., 15 - 30 min), pouring into ice H2O, satd. with NaCl, stirring (2 h); filtration, washing, (15 % aq. KI, satd. aq. NaCl, H2O, EtOH and ether),drying;	99%

ferrocene (102-54-5) + (E)-4,4-dimethyl-2-pentenoyl chloride (132278-01-4) → E-1-ferrocenyl-4,4-dimethylpent-2-ene-1-one

Conditions

Yield

With AlCl3 In dichloromethane under N2; CH2Cl2 added with stirring to mixt. of Fe complex and AlCl3 (molar ratio 1:1); cooled to -78°C; soln. of t-BuCHCHC(O)Cl (1 equiv.) in CH2Cl2 added dropwise over 30 min; warmed slowly to room temp. over 20 min; quenched by dropwise addition of satd. aq. soln. of Na2S2O4; org. layer sepd.; washed with water and satd. aq. NaCl in air; dried (MgSO4); soln.filtered; volatiles removed in vac.; recrystd. from satd. soln. in hexa ne-Et2O at -30°C; elem. anal.;

99%

ferrocene (102-54-5) + 2-Iodobenzoyl chloride (609-67-6) → (o-Iodobenzoyl)ferrocene (109800-02-4)

Conditions	Yield
With aluminum (III) chloride In dichloromethane at 0 - 20℃; for 0.25h; Friedel-Crafts Acylation; Inert atmosphere; Schlenk technique;	99%
With aluminum (III) chloride In dichloromethane at 20℃; for 3h; Inert atmosphere;	0.243 g
Friedel-Crafts Acylation;

ferrocene (102-54-5) + bis(nonafluoro-tert-butyl) peroxide (26842-85-3) → ferrocenium nonafluoro-tert-butoxide

Conditions	Yield
at 20℃; Schlenk technique;	99%
Schlenk technique; Inert atmosphere;	99%

ferrocene (102-54-5) + N-methyl-N-phenylformamide (93-61-8) → ferrocenecarboxaldehyde (12093-10-6)

Conditions	Yield
Stage #1: N-methyl-N-phenylformamide With trichlorophosphate at 0℃; for 0.25h; Stage #2: ferrocene at 20℃; Inert atmosphere;	98%
With phosphorus oxychloride In neat (no solvent) anilide and P-compd. stirring at room temp. for 30 min, Fe-compd. addn.,mixt. stirring at room temp. for 3 d, quenching by pouring onto ice, aq . layer extn. after 2 h with Et2O, org. layer drying (MgSO4), vac. concn.; residue flash column chromy. (SiO2, petrol/E2O 7:3 to 5:5), recrystn. (hot petroleum);	87%
With trichlorophosphate In neat (no solvent) Vilsmeyer formylation; double mol amt. of formylation mixt., few days at ambient temp.;;	81%

ferrocene (102-54-5) + propionic acid anhydride (123-62-6) → propionylferrocene

Conditions	Yield
With boron trifluoride diethyl etherate In dichloromethane ferrocene and 2 equivs. of acid anhydride suspended in CH2Cl2 and cooledto 0°C, boron trifluoride etherate added over 10 min, stirred at room temp. for 3 h; poured into ice H2O, sepd., the org. layer washed (satd. NaHCO3 soln.), dried (MgSO4), solvent-removed, flash-chromd. (SiO2, cyclohexane/EtOAc);	98%
With aluminum (III) chloride In chloroform at 4 - 40℃; for 1h; Friedel-Crafts Acylation;	87%
With polyphosphoric acid In propionic acid anhydride Ar-atmosphere; addn. of excess of anhydride to Fe-complex soln., addn. of polyphosphoric acid, heating to 100°C for 15 min; pouring into ice water, neutralization (aq. Na2CO3), extn. into ether, washing of org. phase (H2O), drying (MgSO4), filtration, concn. (vac.), chromy. (SiO2, ether/pentane=1:3);	80%

butanoic acid anhydride (106-31-0) + ferrocene (102-54-5) → 1-butanoylferrocene

Conditions	Yield
With boron trifluoride diethyl etherate In dichloromethane ferrocene and 2 equivs. of acid anhydride suspended in CH2Cl2 and cooledto 0°C, boron trifluoride etherate added over 10 min, stirred at room temp. for 3 h; poured into ice H2O, sepd., the org. layer washed (satd. NaHCO3 soln.), dried (MgSO4), solvent-removed, flash-chromd. (SiO2, cyclohexane/EtOAc);obtained as oil;	98%
With aluminum (III) chloride In chloroform at 4 - 40℃; for 1h; Friedel-Crafts Acylation;	84%
With aluminum oxide In dichloromethane stirring (30 min); extraction (water, Et2O), chromy.;	60%

Upstream product

• 7705-08-0 iron(III) chloride 
• 63757-86-8 magnesium cyclopentadienide 
• 34822-90-7 cyclopentadienylthallium 
• 100-51-6 benzyl alcohol 
• 12152-94-2 1,1′-ferrocenediboronic acid 
• 1277-58-3 1-(2,2-dimethylpropyl)ferrocenium 

Downstream Products

• 38959-35-2 η-fluorene-η-cyclopentadienyliron(II) hexafluorophosphate 
• 38117-78-1 η-biphenyl-η-cyclopentadienyliron(II) hexafluorophosphate 
• 86731-50-2 η-benzhydrol-η-cyclopentadienyliron(II) hexafluorophosphate 
• 12125-80-3 ferrocenium 
• 45847-02-7 cumyl hydroperoxide anion 
• 12093-10-6 ferrocenecarboxaldehyde 
• 1271-55-2 acetylferrocene 
• 1273-74-1 chloroferrocene 
• 1282-37-7 ferrocenium(III) tetrafluoroborate 
• 7440-44-0 pyrographite 
• 7722-84-1 dihydrogen peroxide 
• 1271-48-3 1,1'-ferrocenyldicarboxaldehyde 
• 1271-42-7 ferrocenecarboxylic acid 

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Relevant articles and documents

Homoleptic complexes of cobalt(0) and nickel(0,I) with 1,1′- bis(diphenylphosphino)ferrocene (dppf): Synthesis and characterization

Reduction of Co(dppf)Cl2 with 2 equiv of sodium naphthalenide in THF, in the presence of dppf, affords the homoleptic complex Co(dppf) 2, 1, isolated in 65% yield as a brick red solid, extremely air sensitive. In solution, under inert atmosphere, 1 slowly decomposes into Co and dppf, following a first-order kinetic law (t1/2 = 21 h at 22°C). Similarly to the Rh and Ir congeners, 1 undergoes a one-electron reversible reduction to [Co(dppf)2]-. Attempts to obtain this d 10 species by chemical as well as electrochemical reduction of 1 lead to the hydride HCo(dppf)2, 2, as the only product that can be isolated. Reduction of Ni(dppf)Cl2 with sodium in the presence of dppf and catalytic amounts of naphthalene affords Ni(dppf)2, 3, isolated in 60% yield as a yellow air stable solid. The stoichiometric oxidation of 3 with [FeCp2]PF6 forms the d9 complex [Ni(dppf)2]PF6, 4, which represents the second example of a structurally characterized Ni(I) complex stabilized by phosphines. A single-crystal X-ray analysis shows for the metal a distorted tetrahedral environment with a dihedral angle defined by the planes containing the atoms P(1), Ni, P(2) and P(3), Ni, P(4) of 78.2° and remarkably long Ni-P bond distances (2.342(3)-2.394(3) A). The EPR spectroscopic properties of 1 (at 106 K in THF) and 4 (at 7 K in 2-methyl-THF) have been examined and g tensor values measured (1, gx = 2.008, gy = 2.182, gz = 2.326; 4, gx = 2.098, gy = 2.113, gz = 2.332). A linear dependence between the hyperfine constants and the Ni-P bond distances has been evidenced. Finally, the change with time of the EPR spectrum of 4 indicates that it very slowly releases dppf.

Reactivity of an early-late heterobimetallic complex toward phosphines: Synthesis, structure, and reactivity of a cationic tantalum-palladium compound with a free cyclopentadienyl counteranion

Treatment of Cp2Ta(CH2)(CH3) with CpPd-(C3H5) led to Cp2Ta(μ-CH2)2PdCp(1). Reaction of 1 with 1 equiv of either PMe3 or P(OMe)3 in CH2Cl2 resulted in the formation of Cp2Ta(μ-CH2)2Pd(PR3)(Cl) (R = Me, 2; R = OMe, 3) and 0.5 equiv of Cp2(CH2). The reaction of 1 with 2 equiv of PMe3 or P(OMe)3 or 1 equiv of Me2P(CH2)2PMe2 (DMPE) led to the isolation of [Cp2-Ta(μ-CH2)2PdL2]Cl (L2 = 2 PMe3, 4; L2 = 2 P(OMe)3, 5; L2 = DMPE, 6). Addition of P(OMe)3 to 1 in CH3CN gave the product Cp2Ta(μ-CH2)2Pd(P(OMe)3)(CH 2CN) (7). Each of these reactions of 1 with phosphorus compounds implicates the intermediacy of free cyclopentadienyl onion. In support of this hypothesis, the stable naked Cp complex [Cp2Ta(μ-CH2)2Pd(DMPE)]Cp (8) was isolated from the reaction of 1 with DMPE in CH3CN and was characterized by X-ray crystallography. The shortest distance between the free anionic Cp group and the bimetallic fragment in 8 is 3.46(3) A. Addition of FeCl2 to 8 resulted in the formation of 1/2 equiv of Cp2Fe and 6. Treatment of 8 with 1,2-dibromoethane led to the quantitative formation of 1/2 equiv of spiro[2.4]hepta-4,6-diene together with the bromide salt of 8.

Unusual reactivities of (μ-η2:η2-FP-CC-H)Co2(CO)6, the adducts of FP-CC-H to Co2(CO)8: photolysis, thermolysis and reduction with hydrosilanes giving polynuclear complexes, (CP)2Fe2Co3(μ5-C=CH)(CO)10, (μ-CH=CH)3-C)Co3(CO)9>2 and CpFeCo3(μ-C=CH2)(CO)9

The properties and reactivities of (μ-η2:η2-FP-CC-H)Co2(CO)6 (3) C-H adducts to Co2(CO)8: 3a (FP = Fp), 3b (FP = Fp*)> have been compared with those of alkyne adducts (μ-η2:η2-R-CC-R)Co2(CO)6 and the Ph analogue (μ-η2:η2-Fp-CC-Ph)Co2(CO)6 (5).Compound 3 has been shown to serve as a building block for polynuclear complexes. 13CO-labelling experiments on 3a and 5 have revealed an intramolecular exchange between the Fe-CO and Co-CO ligands.Photolysis of 3a, b produces pentanuclear clusters (CP)2Fe2Co3(μ5-C=CH)(CO)10 (11a,b), respectively, via an apparent addition reaction of a (CP)FeCo(CO)n fragment to 3.On the other hand, thermolysis of 3a gives the Fe-free hexacobalt cluster compound (μ-C=CH)3-C)Co3(CO)9>2 (13) which consists of two alkylidyne tricobalt units linked by the CH=CH bridge, whereas 3b is thermolyzed to give the Fe-Co dimer without the C2H ligand, Cp*Fe(CO)(μ-CO)2Co(CO)3 (14), in addition to the photolysis product 11b.Reduction of 3 with hydrosilanes gives a mixture containing 1,2-disilylethylene (16) and the tetranuclear μ-vinylidene cluster CpFeCo3(μ4-C=CH2)(CO)9 (12) formally by way of hydrosilylation and hydrometallation (with a HCo(CO)n species) of the C2H ligand, respectively.In the case of the Pauson-Khand reaction and catalytic cyclotrimerization 3a exhibits reactivities similar to alkyne adducts to give the tricyclic cyclopentenone derivatives 18 (from norbornene and norbornadiene) and triphenylbenzenes, respectively. Key words: Iron; Cobalt; Carbonyl; Polynuclear

THE APPLICATION OF 13C AND 1H NMR SPECTROSCOPY TO THE INVESTIGATION OF THE DINITROGEN FIXATION PROCESS IN THE SYSTEM (η-C5H5)2TiCl2-Mg

The N2 reduction reaction in the system (η-C5H5)2TiCl2-Mg in tetrahydrofuran was examined.The 13C and 1H NMR results as well as the chemical properties of the products formed revealed that the reaction yielded a mixture of compounds in which the titanium atom was bonded both to the μ-(η5: η5-fulvalene) ligand and to the cyclopentadienyl ligands.In this system dinitrogen undergoes reduction to N3-, which then forms M3N bridges (M = Ti, Mg).The nitride nitrogen may readily be oxidized to imide nitride N-1, which may react further, e.g. with carbon monoxideto produce isocyanates, or, with excess oxidizing agent N2.THF in this system undergoes polymerisation.In addition, a - OC4H9 alkoxy group is formed which makes the substitution of the cyclopentadienyl group bonded to the titanium atoms possible.

δ-Ferrocenyl-Komplexe des Rutheniums

The reactions of lithioferrocene (fcLi) and 1,1'-dilithioferrocene (FcLi2) with the halfsandwich ruthenium complexes CpRu(CO)2Cl, Cp*Ru(CO)2Cl and (C6Me6)Ru(CO)Cl2 have been used to prepare the ferrocenyl compounds CpRu(CO)2Fc (1), Cp*Ru(CO)2Fc (2) and (C6Me6)Ru(CO)(Cl)Fc (3), as well as the ferrocenylene compounds 2fc (4) and *Ru(CO)2>2fc (5), respectively. Photodecarbonylation of 1 and 2 in the presence of two-electron ligands (L = CNtBu (a), PPh3 (b), PMe3 (c)) leads to chiral complexes of the type Cp(*)Ru(CO)(L)Fc (1a-c, 2a-c); in the case of L = CNtBu, further CO-substitution takes place to give Cp(*)Ru(CNtBu)2Fc (1d, 2d).Photo-induced reaction of 3 with excess trimethylphosphane, PMe3 (c), produces the octahedral complex mer- (6), whereas organolithiums (nBuLi and p-TolLi, but not FcLi) react with 3 to give (C6Me6)Ru(CO)(R)Fc (R = nBu (7a), p-Tol (7b)).Oxidation of 1, 2 and 3 by AgBF4 leads to paramagnetic salts such as (*)Ru(CO)2Fc>BF4 (1e, 2e) and BF4 (3e).All new complexes were characterized by IR, 1H and 13C NMR, and mass spectroscopy; the Cp and Cp* compounds were also studied by cyclovoltammetry.

Chemistry of cyclopentadienyliron dicarbonyl dimer and ferrocene in zeolite Y cavities: Anchoring organometallic fragments into microporous solids

The intracavity chemistry of [CpFe(CO)2]2 (1) and ferrocene in different acid forms of zeolite Y has been studied with EXAFS, in situ FTIR, and TPD-MS spectroscopies. Depending on the stoichiometry of zeolite protons vs the amount of

An electrochemical study of the reduction of mono- and bis(iron) cyclophane complexes

The electrochemical reduction of six [(η5-C5H5)Fe(η 6-cyclophane)]+PF6- and four {[(η5-C5H5)Fe] 2(cyclophane)}2+(PF6/

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Synthesis and characterization of oxidized W6S8L6 clusters

Cationic [W6S8L6]PF6 (L = PEt3 (3), 4-tert-butylpyridine (4)) clusters were successfully synthesized and isolated for the first time by reacting the corresponding neutral W6S8L6 (L = PEt3 (1), 4-tert-butylpyridine (2)) clusters with [Cp2Fe]PF6 as the oxidant. The products 3 and 4 were characterized by NMR spectroscopy, mass spectroscopy, and X-ray crystallography (only for 3) and shown to be the desired oxidized W6S8 clusters with a metal electron count of 19. Magnetic property studies showed that they are paramagnetic compounds with S = 1/2. Their chemical properties and stability are also reported. Crystal data for 3·2THF: space group, R3 (No. 148); a = 13.91170(10) A; c = 32.4106(2) A; Z = 3.

The synthesis, aromaticity, and NMR properties of [14]annulene fused organometallics. Determination of the effective bond localizing ability ('relative aromaticity') and diamagnetic anisotropy of several organometallic moieties

The aromatic ring current probe, the bridged [14]annulene dimethyldihydropyrene, 1, is used to investigate the bond localization effects of the organometallic species tricarbonylchromiumbenzene, 37, hexamethylbenzenerutheniumbenzene, 38, tricarbonylmanganesecyclopentadienyl, 40, and pentamethylcyclopentadienylrutheniumcyclopentadienyl, 39, when fused to the annulene. Benzo[a]dimethyldihydropyrene 2 was converted to the two isomers of its tricarbonylchromium complex, 9 and 10, in 60% yield using ligand exchange with naphthalene and to its hexamethylbenzene-ruthenium complexes 11 and 12 with [RuCl2(HMB)]2 and AgBF4. The cyclopentadienide fused dihydropyrene 5 was synthesized from dimethyldihydropyrene 1 in eight steps, and then on reaction with pentacarbonyl manganese bromide gave the tricarbonylmanganese complex of 5, as two isomers 28 and 29 in 61% yield, and with (Cp*RuCl2)(n) gave 70% yield of the dihydropyrene annelated ruthenocene isomers 26 and 27. Bis(tricarbonylchromium) complexes 32-34 were obtained in 50% yield from the dibenzannulene 30. The 1H NMR spectra for each complex were analyzed in detail with regard to ring current shielding of the internal methyl protons and ring current deshielding of the external protons. The McGlinchey equation was used to remove diamagnetic anisotropy effects, and the resultant chemical shift values were consistent with coupling constant results, which together yielded bond fixation data of the annulene, caused by the organometallic. The relative bond fixing ability of the organometallics was found to be in the order: Cp-Ru-Cp* > benzene-Ru2+-(HMB) > Cp-Mn(CO)3 > benzene-Cr(CO)3 > benzene. Alternance parameter evidence is presented that the complexes are aromatic, and the authors discuss the relative aromaticity of the complexes to benzene.

Sequential Friedel-Crafts diacetylation of ferrocene: Interannular proton transfers as a mechanistic probe

(Pentadeuteriocyclopentadienyl)cyclopentadienyliron(II), 4, was prepared by the sequential addition of lithium tris(trimethylsilyl)cyclopentadienide and lithium pentadeuteriocyclopentadienide to FeBr2 followed by fluoride-induced removal of the trimethylsilyl groups of the resulting ferrocene 3. Analysis of the deuterium content of the acetylferrocene 5 and the 1,1′-diacetylferrocene 7, obtained from the Friedel-Crafts acetylation of 4, reveals that the former is formed by initial exo attack of AlCl3-CH3COCl, whereas precomplexation of the electrophile at the metal center (endo attack) precedes the formation of the latter.

Dicationic Thiolate-Bridged Diruthenium Complexes for Catalytic Oxidation of Molecular Dihydrogen

Dicationic thiolate-bridged diruthenium complexes bearing sterically bulky alkane substituents on the thiolate ligands such as [Cp?Ru(μ-SiPr)2Ru(OH2)Cp?](OTf)2 have been found to work as effective catalysts toward oxidation of molecular dihydrogen into protons and electrons in protic solvents such as water and methanol. DFT calculations indicate that the sterically bulky alkane substituent in the complex plays an important role in facilitating the reaction step of the coordination of molecular dihydrogen.

Oxidation of Ascorbic Acid by Copper(II) and the Ferrocenium Ion in Acetonitrile-Water Mixtures

Measurements are reported on the rates of oxidation of ascorbic acid (H2A) by copper(II) and the ferrocenium cation + in mixtures of water and acetonitrile.The stabilisation of Cu+ by acetonitrile results in a rapid increase in E0 for Cu2+ - Cu+ and simple, irreversible reaction between copper(II) and ascorbic acid to form copper(I) and dehydroascorbic acid upon addition of small amounts of acetonitrile to water.The acid dependence of the rate constant is consistent with the involvement of complexes of the monoanion, II(HA)>+, and the dianion IIA>, the former becoming relatively more important with increasing acetonitrile content of the solvent.The solvent dependence of the rate constant is discussed in relation to the solvation of copper(II) and copper(I) in the mixtures and it is suggested that the dominant influence is the solvation of copper(I) formed in the initial electron-transfer process.Redox potentials, E for + - , and rates of oxidation of ascorbic acid by ferrocenium, a typical outer-sphere oxidant, have been measured under the same conditions and are compared with those of the copper(II) - copper(I) system.

Catalytic Activity of Thiolate-Bridged Diruthenium Complexes Bearing Pendent Ether Moieties in the Oxidation of Molecular Dihydrogen

Thiolate-bridged diruthenium complexes bearing pendent ethers have been found to work as effective catalysts toward the oxidation of molecular dihydrogen into protons and electrons in water. The pendent ether moiety in the complex plays an important role to facilitate the proton transfer between the metal center and the external proton acceptor.

Naphthocage: A Flexible yet Extremely Strong Binder for Singly Charged Organic Cations

We report a quite flexible naphthol-based cage (so-called "naphthocage") which adopts a self-inclusion conformation in its free state and is able to bind singly charged organic cations extremely strongly (Ka > 107 M-1). Ion-selective electrodes prepared with this naphthocage show a super-Nernstian response to acetylcholine. In addition, the highly stable complex (1010 M-1) between ferrocenium and the naphthocage can be switched electrochemically, which lays a basis for its application in stimuli-responsive materials.

A Study of the reaction of iron dichloride with the pyridine activated cyclopentadiene in anhydrous 2-propanol

A reaction was studied between iron dichloride solvate and pyridine activated cyclopentadiene in anhydrous 2-propanol. We showed that pyridine hydrochloride formed in the course of this reaction can be easily separated from the target product (ferrocene) and recycled after neutralization with sodium isopropoxide, which imparts the preparative value to the studied reaction.

Photoresist based on metallocene compound and preparation method and application thereof

The invention belongs to the technical field of photoresist, and particularly relates to a photoresist based on a metallocene compound as well as a preparation method and application of the photoresist. The metallocene compound disclosed by the invention adopts metal as a central core structure, so that the metallocene compound has a relatively high melting point and glass-transition temperature, can meet the requirements of a photoetching technology, and is stable in structure, and a film structure is not changed during high-temperature baking. In addition, the photoresist composition provided by the invention can be used in modern photoetching processes such as 248nm photoetching, 193nm photoetching, extreme ultraviolet (EUV) photoetching, nanoimprint lithography (NIL), electron beam lithography (EBL) and the like, and is particularly suitable for being used in an extreme ultraviolet (EUV) photoetching process.

A Mononuclear Non-heme Iron(III)-Peroxo Complex with an Unprecedented High O-O Stretch and Electrophilic Reactivity

A mononuclear non-heme iron(III)-peroxo complex, [Fe(III)(O2)(13-TMC)]+ (1), was synthesized and characterized spectroscopically; the characterization with electron paramagnetic resonance, M?ssbauer, X-ray absorption, and resonance Raman spectroscopies and mass spectrometry supported a high-spin S = 5/2 Fe(III) species binding an O2 unit. A notable observation was an unusually high νO-O at ～1000 cm-1 for the peroxo ligand. With regard to reactivity, 1 showed electrophilic reactivity in H atom abstraction (HAA) and O atom transfer (OAT) reactions. In the HAT reaction, a kinetic isotope effect (KIE) value of 5.8 was obtained in the oxidation of 9,10-dihydroanthracene. In the OAT reaction, a negative ρ value of -0.61 in the Hammett plot was determined in the oxidation of p-X-substituted thioanisoles. Another interesting observation was the electrophilic reactivity of 1 in the oxidation of benzaldehyde derivatives, such as a negative ρ value of -0.77 in the Hammett plot and a KIE value of 2.2. To the best of our knowledge, the present study reports the first example of a mononuclear non-heme iron(III)-peroxo complex with an unusually high νO-O value and unprecedented electrophilic reactivity in oxidation reactions.

Imidazolium Cyclopentadienide Salts and their Use as Cp-Transfer Reagents

The reaction of N-heterocyclic carbenes, 1a–c, towards cyclopentadienes, 2a–c, was studied. N,N′-diisopropyl-substituted carbene 1a acts as a Br?nsted base and deprotonates cyclopentadiene, 2a, and isopropylcyclopentadiene, 2b, to yield the corresponding imidazolium cyclopentadienide salts, 3a,b, whereas there is no reaction towards 1,2,3,4,5-pentamethylcyclopentadiene. Imidazolium cyclopentadienide salts, 3a,b, were characterized in solution by 1H and 13C NMR spectroscopy, as well as in the solid state by single-crystal X-ray diffraction. In addition, it was demonstrated that imidazolium cyclopentadienide salt 3a can be used as a Cp-transfer reagent in the synthesis of different cyclopentadienyl transition metal complexes.