(Diene)iron tricarbonyl

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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.

Contents

Scope

structure of the Fe(CO)3 adduct of vitamin A aldehyde. VitaminAaldehydeFe(CO)3.svg
structure of the Fe(CO)3 adduct of vitamin A aldehyde.

The inventory of complexes is large.

Selected (diene)Fe(CO)3 Complexes
dieneCAS RNphysical propertiesnotes
(cyclobutadiene)Fe(CO)3 12078-17-0orange solid, b.p. 47 °C (3 mm) antiaromatic ligand [2]
(butadiene)Fe(CO)3 12078-32-9yellow-orange, m.p. 19 °Cmajor prototype
(Isoprene)Fe(CO)332731-93-4yellow liquidchiral [3]
(1,3-Cyclohexadiene)Fe(CO)312252-72-6yellow, m.p. 8-9 °Cmajor prototype for steroidal and terpenoid derivatives [4]
(norbornadiene)Fe(CO)312307-07-2yellow, m.p. -2 °Cnon-conjugated diene [5]
(norbornadienone)Fe(CO)312307-01-6yellow, m.p. 93-95 °Cfree diene-one is unstable [6]
(1,5-Cyclooctadiene)Fe(CO)312093-20-8yellow, m.p. 76 °Cnon-conjugated diene [7] [8]
(1,3-Cyclooctadiene)Fe(CO)333270-50-7yellow, m.p. 36 °Cisomeric with 1,5-cyclooctadiene derivative [7] [9]
4-Thiepine)Fe(CO)3-yellow, , m.p. 54.5-55 °Cchiral, thiepine = cyclo-C6H6S, which is antiaromatic [10]

Preparation and uses

Many of diene complexes were originally prepared by reaction of iron pentacarbonyl with the diene under UV-radiation. Often yields are modest because the complexes, which are often liquids, volatilize during workup. [5] Some derivatives derivatives are prepared displacement of bda from (benzylideneacetone)iron tricarbonyl (Fe(bda)(CO)3) [11]

The Fe(CO)3 unit serves as a protecting group for the diene, preventing the diene from participating in Diels-Alder reactions and hydrogenation. The diene is usually deprotected with ceric ammonium nitrate. [12]

These complexes are mainly of academic interest. Some iron tricarbon complexes of cyclopentadienones catalyze hydrogenation, see Knolker complex.

Characterization

Sample of (butadiene)Fe(CO)3, illustrating the color typical of this family of compounds. ButadieneFe(CO)3.jpg
Sample of (butadiene)Fe(CO)3, illustrating the color typical of this family of compounds.

IR spectra of these complexes show νCO bands near 2040 and 1969 cm-1. At low temperatures, the lower energy band splits, which has been interpreted as evidence for fluxionality on the IR timescale. [13]

Related Research Articles

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

1,3,5,7-Cyclooctatetraene (COT) is an unsaturated derivative of cyclooctane, with the formula C8H8. It is also known as [8]annulene. This polyunsaturated hydrocarbon is a colorless to light yellow flammable liquid at room temperature. Because of its stoichiometric relationship to benzene, COT has been the subject of much research and some controversy.

<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.

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

In organic chemistry, thiepine (or thiepin) is an unsaturated seven-membered heterocyclic compound, with six carbon atoms and one sulfur atom. The parent compound, C6H6S is unstable and is predicted to be antiaromatic. Bulky derivatives have been isolated and shown by X-ray crystallography to have nonplanar C6S ring.

Osmium compounds are compounds containing the element osmium (Os). Osmium forms compounds with oxidation states ranging from −2 to +8. The most common oxidation states are +2, +3, +4, and +8. The +8 oxidation state is notable for being the highest attained by any chemical element aside from iridium's +9 and is encountered only in xenon, ruthenium, hassium, iridium, and plutonium. The oxidation states −1 and −2 represented by the two reactive compounds Na
2
[Os
4
(CO)
13
]
and Na
2
[Os(CO)
4
]
are used in the synthesis of osmium cluster compounds.

<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">Sandwich compound</span> Chemical compound made of two ring ligands bound to a metal

In organometallic chemistry, a sandwich compound is a chemical compound featuring a metal bound by haptic, covalent bonds to two arene (ring) ligands. The arenes have the formula CnHn, substituted derivatives and heterocyclic derivatives. Because the metal is usually situated between the two rings, it is said to be "sandwiched". A special class of sandwich complexes are the metallocenes.

<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">Triosmium dodecacarbonyl</span> Chemical compound

Triosmium dodecacarbonyl is a chemical compound with the formula Os3(CO)12. This yellow-colored metal carbonyl cluster is an important precursor to organo-osmium compounds. Many of the advances in cluster chemistry have arisen from studies on derivatives of Os3(CO)12 and its lighter analogue Ru3(CO)12.

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

Triruthenium dodecacarbonyl is the chemical compound with the formula Ru3(CO)12. Classified as metal carbonyl cluster, it is a dark orange-colored solid that is soluble in nonpolar organic solvents. The compound serves as a precursor to other organoruthenium compounds.

Organoiron chemistry is the chemistry of iron compounds containing a carbon-to-iron chemical bond. 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. 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.

<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.

Metal acetylacetonates are coordination complexes derived from the acetylacetonate anion (CH
3
COCHCOCH
3
) and metal ions, usually transition metals. The bidentate ligand acetylacetonate is often abbreviated acac. Typically both oxygen atoms bind to the metal to form a six-membered chelate ring. The simplest complexes have the formula M(acac)3 and M(acac)2. Mixed-ligand complexes, e.g. VO(acac)2, are also numerous. Variations of acetylacetonate have also been developed with myriad substituents in place of methyl (RCOCHCOR). Many such complexes are soluble in organic solvents, in contrast to the related metal halides. Because of these properties, acac complexes are sometimes used as catalyst precursors and reagents. Applications include their use as NMR "shift reagents" and as catalysts for organic synthesis, and precursors to industrial hydroformylation catalysts. C
5
H
7
O
2
in some cases also binds to metals through the central carbon atom; this bonding mode is more common for the third-row transition metals such as platinum(II) and iridium(III).

<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">Transition-metal allyl complex</span>

Transition-metal allyl complexes are coordination complexes with allyl and its derivatives as ligands. Allyl is the radical with the connectivity CH2CHCH2, although as a ligand it is usually viewed as an allyl anion CH2=CH−CH2, which is usually described as two equivalent resonance structures.

<span class="mw-page-title-main">Transition metal nitrile complexes</span> Class of coordination compounds containing nitrile ligands (coordinating via N)

Transition metal nitrile complexes are coordination compounds containing nitrile ligands. Because nitriles are weakly basic, the nitrile ligands in these complexes are often labile.

<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">Transition metal isocyanide complexes</span> Class of chemical compounds

Transition metal isocyanide complexes are coordination compounds containing isocyanide ligands. Because isocyanides are relatively basic, but also good pi-acceptors, a wide range of complexes are known. Some isocyanide complexes are used in medical imaging.

Trimethylenemethane complexes are metal complexes of the organic compound trimethylenemethane. Several examples are known, and some have been employed in organic synthesis.

References

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