Organoiron chemistry

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Organoiron chemistry is the chemistry of iron compounds containing a carbon-to-iron chemical bond. [1] [2] Organoiron compounds are relevant in organic synthesis as reagents such as iron pentacarbonyl, diiron nonacarbonyl and disodium tetracarbonylferrate. Although iron is generally less active in many catalytic applications, it is less expensive and "greener" than other metals. [3] Organoiron compounds feature a wide range of ligands that support the Fe-C bond; as with other organometals, these supporting ligands prominently include phosphines, carbon monoxide, and cyclopentadienyl, but hard ligands such as amines are employed as well.

Contents

Iron(–II) and Iron(0)

Iron pentacarbonyl. Sample of iron pentacarbonyl.jpg
Iron pentacarbonyl.

Carbonyl complexes

Important iron carbonyls are the three neutral binary carbonyls, iron pentacarbonyl, diiron nonacarbonyl, and triiron dodecacarbonyl. One or more carbonyl ligands in these compounds can be replaced by a variety of other ligands including alkenes and phosphines. An iron(-II) complex, disodium tetracarbonylferrate (Na2[Fe(CO)4]), also known as "Collman's Reagent," is prepared by reducing iron pentacarbonyl with metallic sodium. The highly nucleophilic anionic reagent can be alkylated and carbonylated to give the acyl derivatives that undergo protonolysis to afford aldehydes: [4]

LiFe(CO)4(C(O)R) + H+ → RCHO (+ iron containing products)

Similar iron acyls can be accessed by treating iron pentacarbonyl with organolithium compounds:

ArLi + Fe(CO)5 → LiFe(CO)4C(O)R

In this case, the carbanion attacks a CO ligand. In a complementary reaction, Collman's reagent can be used to convert acyl chlorides to aldehydes. Similar reactions can be achieved with [HFe(CO)4]− salts. [5]

Alkene-Fe(0)-CO derivatives

(Butadiene)iron tricarbonyl. (Butadiene)iron-tricarbonyl-3D-balls.png
(Butadiene)iron tricarbonyl.

Monoalkenes

Iron pentacarbonyl reacts photochemically with alkenes to give Fe(CO)4(alkene). [6]

Diene-Fe(0)-CO derivatives

Iron diene complexes are usually prepared from Fe(CO)5 or Fe2(CO)9. Derivatives are known for common dienes like cyclohexadiene, [7] norbornadiene and cyclooctadiene, but even cyclobutadiene can be stabilized. In the complex with butadiene, the diene adopts a cis-conformation. Iron carbonyls are potential protective groups for dienes, shielding them from hydrogenations and Diels-Alder reactions. Cyclobutadieneiron tricarbonyl is prepared from 3,4-dichlorocyclobutene and Fe2(CO)9.

Cyclohexadienes, many derived from Birch reduction of aromatic compounds, form derivatives (diene)Fe(CO)3. The affinity of the Fe(CO)3 unit for conjugated dienes is manifested in the ability of iron carbonyls catalyse the isomerisations of 1,5-cyclooctadiene to 1,3-cyclooctadiene. Cyclohexadiene complexes undergo hydride abstraction to give cyclohexadienyl cations, which add nucleophiles. Hydride abstraction from cyclohexadiene iron(0) complexes gives ferrous derivatives. [8] [9]

The enone complex (benzylideneacetone)iron tricarbonyl serves as a source of the Fe(CO)3 subunit and is employed to prepare other derivatives. It is used similarly to Fe2(CO)9.

Alkyne-Fe(0)-CO derivatives

Alkynes react with iron carbonyls to give a large variety of derivatives. Derivatives include ferroles (Fe2(C4R4)(CO)6), (p-quinone)Fe(CO)3, (cyclobutadiene)Fe(CO)3 and many others. [10]

Tri- and polyene Fe(0) complexes

Stable iron-containing complexes with and without CO ligands are known for a wide variety of polyunsaturated hydrocarbons, e.g. cycloheptatriene, azulene, and bullvalene. In the case of cyclooctatetraene (COT), derivatives include Fe(COT)2, [11] Fe3(COT)3, [12] and several mixed COT-carbonyls (e.g. Fe(COT)(CO)3 and Fe2(COT)(CO)6).

Bis(cyclooctatetraene)iron is an Fe(0) complex lacking CO ligands. Fe(cot)2.svg
Bis(cyclooctatetraene)iron is an Fe(0) complex lacking CO ligands.

Iron(I) and iron(II)

As Fe(II) is a common oxidation state for Fe, many organoiron(II) compounds are known. Fe(I) compounds often feature Fe-Fe bonds, but exceptions occur, such as [Fe(anthracene)2]−. [13]

cyclopentadienyliron dicarbonyl dimer Organoiron.png
cyclopentadienyliron dicarbonyl dimer

Ferrocene and its derivatives

The rapid growth of organometallic chemistry in the 20th century can be traced to the discovery of ferrocene, a very stable compound which foreshadowed the synthesis of many related sandwich compounds. Ferrocene is formed by reaction of sodium cyclopentadienide with iron(II) chloride:

2 NaC5H5 + FeCl2 → Fe(C5H5)2 + 2 NaCl

Ferrocene displays diverse reactivity localized on the cyclopentadienyl ligands, including Friedel–Crafts reactions and lithation. Some electrophilic functionalization reactions, however, proceed via initial attack at the Fe center to give the bent [Cp2Fe–Z]+ species (which are formally Fe(IV)). For instance, HF:PF5 and Hg(OTFA)2, give isolable or spectroscopically observable complexes [Cp2Fe–H]+PF6– and Cp2Fe+–Hg–(OTFA)2, respectively. [14] [15] [16]

Ferrocene is also a structurally unusual scaffold as illustrated by the popularity of ligands such as 1,1'-bis(diphenylphosphino)ferrocene, which are useful in catalysis. [17] Treatment of ferrocene with aluminium trichloride and benzene gives the cation [CpFe(C6H6)]+. Oxidation of ferrocene gives the blue 17e species ferrocenium. Derivatives of fullerene can also act as a highly substituted cyclopentadienyl ligand.

Fp2, Fp−, and Fp+ and derivatives

Fe(CO)5 reacts with cyclopentadiene to give the dinuclear Fe(I) species cyclopentadienyliron dicarbonyl dimer ([FeCp(CO)2]2), often abbreviated as Fp2. Pyrolysis of Fp2 gives the cuboidal cluster [FeCp(CO)]4.

Very hindered substituted cyclopentadienyl ligands can give an isolable monomeric Fe(I) species. For example, Cpi-Pr5Fe(CO)2 (Cpi-Pr5 = i-Pr5C5) has been characterized crystallographically. [18]

Reduction of Fp2 with sodium gives "NaFp", containing a potent nucleophile and precursor to many derivatives of the type CpFe(CO)2R. [19] The derivative [FpCH2S(CH3)2]+ has been used in cyclopropanations. [20] The Fp+ fragment is Lewis acidic and readily forms complexes with ethers, amines, pyridine, etc., as well as alkenes and alkynes in the η2 coordination mode. The complex Fp+(η2-vinyl ether)]+ is a masked vinyl cation. [21] Recently, a methane complex, [Fp(CH4)]+[Al(OC(CF3)3)4]–, was prepared and characterized spectroscopically, using a perfluoroalkoxyaluminate as a non-coordinating counterion and 1,1,1,3,3,3-hexafluoropropane as a non-coordinating solvent. [22]

Fp-R compounds are prochiral, and studies have exploited the chiral derivatives CpFe(PPh3)(CO)acyl. [23]

Alkyl, allyl, and aryl compounds

The simple peralkyl and peraryl complexes of iron are less numerous than are the Cp and CO derivatives. One example is tetramesityldiiron.

tetramesityldiiron is a rare example of a neutral per-organo complex of iron. Fe2mes4.png
tetramesityldiiron is a rare example of a neutral per-organo complex of iron.

Compounds of the type [(η3-allyl)Fe(CO)4]+X− are allyl cation synthons in allylic substitution. [6] In contrast, compounds of the type [(η5-C5H5)Fe(CO)2(CH2CH=CHR)] possessing η1-allyl groups are analogous to main group allylmetal species (M = B, Si, Sn, etc.) and react with carbon electrophiles to give allylation products with SE2′ selectivity. [24] Similarly, allenyl(cyclopentadienyliron) dicarbonyl complexes exhibit reactivity analogous to main group allenylmetal species and serve as nucleophilic propargyl synthons. [25]

Sulfur and phosphorus derivatives

Complexes of the type Fe2(SR)2(CO)6 and Fe2(PR2)2(CO)6 form, usually by the reaction of thiols and secondary phosphines with iron carbonyls. [26] The thiolates can also be obtained from the tetrahedrane Fe2S2(CO)6.

Iron(III)

Alkylation of FeCl3 with methylmagnesium bromide gives [Fe(CH3)4]-, which is thermally labile. [27] Such compounds may be relevant to the mechanism of Fe-catalyzed cross coupling reactions. [28]

Some organoiron(III) compounds are prepared by oxidation of organoiron(II) compounds. A long-known example being ferrocenium [(C5H5)2Fe]+. Organoiron(III) porphyrin complexes are numerous.

Structure of Fe(tetraphenylporphyrin)C6H5. CUHXAEFetppPh.png
Structure of Fe(tetraphenylporphyrin)C6H5.

Iron(IV)

Fe(4-norbornyl)4 is a rare example of a low-spin tetrahedral complex. Fe(4-norbornyl)4.svg
Fe(4-norbornyl)4 is a rare example of a low-spin tetrahedral complex.

In Fe(norbornyl)4, Fe(IV) is stabilized by an alkyl ligand that resists beta-hydride elimination. [30] Surprisingly, FeCy4, which is susceptible to beta-hydride elimination, has also been isolated and crystallographically characterized and is stable at –20 °C. The unexpected stability was attributed to stabilizing dispersive forces as well as conformational effects that disfavor beta-hydride elimination. [31]

Two-electron oxidation of decamethylferrocene gives the dication [Fe(C5Me5)2]2+, which forms a carbonyl complex, [Fe(C5Me5)2(CO)](SbF6)2. [32]

Iron(V, VI, VII)

In 2020, Jeremy M. Smith and coworkers reported crystallographically characterized Fe(V) and Fe(VI) bisimido complexes based on a bidentate bis(carbene)borate ligand. [33] By virtue of the supporting ligand architecture, these species constitute organometallic Fe(V) and Fe(VI) complexes.

In 2024, Karsten Meyer and coworkers reported a crystallographically characterized Fe(VI) nitrido complex, [(TIMMNMes)FeVI(≡N)(F)](PF6)2·CH2Cl2, which bears a tris(N-heterocyclic carbene) ligand (tris[(3-mesityl-imidazol-2-ylidene)methyl]amine). Related Fe(V) complexes were crystallographically characterized in the same study, while an Fe(VII) species that decomposes above –50 °C was characterized by Mössbauer spectroscopy. [34]

Organoiron compounds in organic synthesis and homogeneous catalysis

In industrial catalysis, iron complexes are seldom used in contrast to cobalt and nickel. Because of the low cost and low toxicity of its salts, iron is attractive as a stoichiometric reagent. Some areas of investigation include:

Biochemistry

In the area of bioorganometallic chemistry, organoiron species are found at the active sites of the three hydrogenase enzymes as well as carbon monoxide dehydrogenase.

Further reading

Related Research Articles

<span class="mw-page-title-main">Metallocene</span>

A metallocene is a compound typically consisting of two cyclopentadienyl anions (C
5H−
5, abbreviated Cp) bound to a metal center (M) in the oxidation state II, with the resulting general formula (C5H5)2M. Closely related to the metallocenes are the metallocene derivatives, e.g. titanocene dichloride or vanadocene dichloride. Certain metallocenes and their derivatives exhibit catalytic properties, although metallocenes are rarely used industrially. Cationic group 4 metallocene derivatives related to [Cp2ZrCH3]+ catalyze olefin polymerization.

<span class="mw-page-title-main">Organometallic chemistry</span> Study of organic compounds containing metal(s)

Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and selenium, as well. Aside from bonds to organyl fragments or molecules, bonds to 'inorganic' carbon, like carbon monoxide, cyanide, or carbide, are generally considered to be organometallic as well. Some related compounds such as transition metal hydrides and metal phosphine complexes are often included in discussions of organometallic compounds, though strictly speaking, they are not necessarily organometallic. The related but distinct term "metalorganic compound" refers to metal-containing compounds lacking direct metal-carbon bonds but which contain organic ligands. Metal β-diketonates, alkoxides, dialkylamides, and metal phosphine complexes are representative members of this class. The field of organometallic chemistry combines aspects of traditional inorganic and organic chemistry.

Ferrocene is an organometallic compound with the formula Fe(C5H5)2. The molecule is a complex consisting of two cyclopentadienyl rings sandwiching a central iron atom. It is an orange solid with a camphor-like odor that sublimes above room temperature, and is soluble in most organic solvents. It is remarkable for its stability: it is unaffected by air, water, strong bases, and can be heated to 400 °C without decomposition. In oxidizing conditions it can reversibly react with strong acids to form the ferrocenium cation Fe(C5H5)+2. Ferrocene and the ferrocenium cation are sometimes abbreviated as Fc and Fc+ respectively.

<span class="mw-page-title-main">Cyclopentadienyl complex</span> Coordination complex of a metal and cyclopentadienyl groups

A cyclopentadienyl complex is a coordination complex of a metal and cyclopentadienyl groups. Cyclopentadienyl ligands almost invariably bind to metals as a pentahapto (η5-) bonding mode. The metal–cyclopentadienyl interaction is typically drawn as a single line from the metal center to the center of the Cp ring.

<span class="mw-page-title-main">Iron pentacarbonyl</span> Chemical compound

Iron pentacarbonyl, also known as iron carbonyl, is the compound with formula Fe(CO)5. Under standard conditions Fe(CO)5 is a free-flowing, straw-colored liquid with a pungent odour. Older samples appear darker. This compound is a common precursor to diverse iron compounds, including many that are useful in small scale organic synthesis.

<span class="mw-page-title-main">Metal carbonyl</span> Coordination complexes of transition metals with carbon monoxide ligands

Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. Metal carbonyls are useful in organic synthesis and as catalysts or catalyst precursors in homogeneous catalysis, such as hydroformylation and Reppe chemistry. In the Mond process, nickel tetracarbonyl is used to produce pure nickel. In organometallic chemistry, metal carbonyls serve as precursors for the preparation of other organometallic complexes.

<span class="mw-page-title-main">Cyclobutadieneiron tricarbonyl</span> Chemical compound

Cyclobutadieneiron tricarbonyl is an organoiron compound with the formula Fe(C4H4)(CO)3. It is a yellow oil that is soluble in organic solvents. It has been used in organic chemistry as a precursor for cyclobutadiene, which is an elusive species in the free state.

Iron shows the characteristic chemical properties of the transition metals, namely the ability to form variable oxidation states differing by steps of one and a very large coordination and organometallic chemistry: indeed, it was the discovery of an iron compound, ferrocene, that revolutionalized the latter field in the 1950s. Iron is sometimes considered as a prototype for the entire block of transition metals, due to its abundance and the immense role it has played in the technological progress of humanity. Its 26 electrons are arranged in the configuration [Ar]3d64s2, of which the 3d and 4s electrons are relatively close in energy, and thus it can lose a variable number of electrons and there is no clear point where further ionization becomes unprofitable.

<span class="mw-page-title-main">Triiron dodecacarbonyl</span> Chemical compound

Triiron dodecarbonyl is the organoiron compound with the formula Fe3(CO)12. It is a dark green solid that sublimes under vacuum. It is soluble in nonpolar organic solvents to give intensely green solutions. Most low-nuclearity clusters are pale yellow or orange. Hot solutions of Fe3(CO)12 decompose to an iron mirror, which can be pyrophoric in air.The solid decomposes slowly in air, and thus samples are typically stored cold under an inert atmosphere. It is a more reactive source of iron(0) than iron pentacarbonyl.

<span class="mw-page-title-main">Diiron nonacarbonyl</span> Chemical compound

Diiron nonacarbonyl is an organometallic compound with the formula Fe2(CO)9. This metal carbonyl is an important reagent in organometallic chemistry and of occasional use in organic synthesis. It is a more reactive source of Fe(0) than Fe(CO)5. This micaceous orange solid is virtually insoluble in all common solvents.

<span class="mw-page-title-main">(Benzylideneacetone)iron tricarbonyl</span> Chemical compound

(Benzylideneacetone)iron tricarbonyl is the organoiron compound with the formula (C6H5CH=CHC(O)CH3)Fe(CO)3. It is a reagent for transferring the Fe(CO)3 unit. This red-colored compound is commonly abbreviated (bda)Fe(CO)3.

<span class="mw-page-title-main">Disodium tetracarbonylferrate</span> Chemical compound

Disodium tetracarbonylferrate is the organoiron compound with the formula Na2[Fe(CO)4]. It is always used as a solvate, e.g., with tetrahydrofuran or dimethoxyethane, which bind to the sodium cation. An oxygen-sensitive colourless solid, it is a reagent in organometallic and organic chemical research. The dioxane solvated sodium salt is known as Collman's reagent, in recognition of James P. Collman, an early popularizer of its use.

<span class="mw-page-title-main">Organoruthenium chemistry</span>

Organoruthenium chemistry is the chemistry of organometallic compounds containing a carbon to ruthenium chemical bond. Several organoruthenium catalysts are of commercial interest and organoruthenium compounds have been considered for cancer therapy. The chemistry has some stoichiometric similarities with organoiron chemistry, as iron is directly above ruthenium in group 8 of the periodic table. The most important reagents for the introduction of ruthenium are ruthenium(III) chloride and triruthenium dodecacarbonyl.

A metallacarboxylic acid is a metal complex with the ligand CO2H. These compounds are intermediates in reactions that involve carbon monoxide and carbon dioxide, these species are intermediates in the water gas shift reaction. Metallacarboxylic acids are also called hydroxycarbonyls.

<span class="mw-page-title-main">Cyclopentadienyliron dicarbonyl dimer</span> Chemical compound

Cyclopentadienyliron dicarbonyl dimer is an organometallic compound with the formula [(η5-C5H5)Fe(CO)2]2, often abbreviated to Cp2Fe2(CO)4, [CpFe(CO)2]2 or even Fp2, with the colloquial name "fip dimer". It is a dark reddish-purple crystalline solid, which is readily soluble in moderately polar organic solvents such as chloroform and pyridine, but less soluble in carbon tetrachloride and carbon disulfide. Cp2Fe2(CO)4 is insoluble in but stable toward water. Cp2Fe2(CO)4 is reasonably stable to storage under air and serves as a convenient starting material for accessing other Fp (CpFe(CO)2) derivatives (described below).

<span class="mw-page-title-main">Cyclopentadienyliron dicarbonyl iodide</span> Chemical compound

Cyclopentadienyliron dicarbonyl iodide is an organoiron compound with the formula (C5H5)Fe(CO)2I. It is a dark brown solid that is soluble in common organic solvents. (C5H5)Fe(CO)2I, or FpI as it is often known, is an intermediate for the preparation of other organoiron compounds such as in ferraboranes.

<span class="mw-page-title-main">Half sandwich compound</span> Class of coordination compounds

Half sandwich compounds, also known as piano stool complexes, are organometallic complexes that feature a cyclic polyhapto ligand bound to an MLn center, where L is a unidentate ligand. Thousands of such complexes are known. Well-known examples include cyclobutadieneiron tricarbonyl and (C5H5)TiCl3. Commercially useful examples include (C5H5)Co(CO)2, which is used in the synthesis of substituted pyridines, and methylcyclopentadienyl manganese tricarbonyl, an antiknock agent in petrol.

<span class="mw-page-title-main">(Butadiene)iron tricarbonyl</span> Chemical compound

(Butadiene)iron tricarbonyl is an organoiron compound with the formula (C4H6)Fe(CO)3. It is a well-studied metal complex of butadiene. An orange-colored viscous liquid that freezes just below room temperature, the compound adopts a piano stool structure.

<span class="mw-page-title-main">Ferrole</span>

In organoiron chemistry, a ferrole is a type of diiron complex containing the (OC)3FeC4R4 heterocycle that is pi-bonded to a Fe(CO)3 group. These compounds have Fe-Fe bonds (ca. 252 pm) and semi-bridging CO ligands (Fe-C distances = 178, 251 pm). They are typically air-stable, soluble in nonpolar solvents, and red-orange in color.

In organometallic chemistry, (diene)iron tricarbonyl describes a diverse family of related coordination complexes consisting of a diene ligand coordinated to a Fe(CO)3 center. Often the diene is conjugated, e.g., butadiene, but the family includes nonconjugated dienes as well. The compounds are yellow, air-stable, often low-melting, and soluble in hydrocarbon solvents. The motif is so robust that even unstable dienes form easily characterized derivatives, such as norbornadienone and cyclobutadiene.

References

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