From Wikipedia, the free encyclopedia - View original article
Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. They occur as neutral complexes, as positively charged metal carbonyl cations or as negatively charged metal carbonylates. The carbon monoxide ligand may be bond terminally to a single metal atom or bridging to two or more metal atoms. These complexes may be homoleptic, that is containing only CO ligands, such as nickel carbonyl (Ni(CO)4), but more commonly metal carbonyls are heteroleptic and contain a mixture of 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 carbonyl is used to produce pure nickel. In organometallic chemistry, metal carbonyls serve as precursors for the preparation of other organometalic complexes.
Carbon monoxide bonds to transition metals using "synergistic π* back-bonding." The bonding has three components, giving rise to a partial triple bond. A sigma bond arises from overlap of nonbonding sp-hybridized electron pair on carbon with a blend of d-, s-, and p-orbitals on the metal. A pair of π bonds arises from overlap of filled d-orbitals on the metal with a pair of π-antibonding orbitals projecting from the carbon of the CO. The latter kind of binding requires that the metal have d-electrons, and that the metal is in a relatively low oxidation state (<+2) which makes the back donation process favorable. As electrons from the metal fill the π-antibonding orbital of CO, they weaken the carbon-oxygen bond compared with free carbon monoxide, while the metal-carbon bond is strengthened. Because of the multiple bond character of the M-CO linkage, the distance between the metal and carbon is relatively short, often < 1.8 Â, about 0.2 Â shorter than a metal-alkyl bond. Several canonical forms can be drawn to describe the approximate metal carbonyl bonding modes.
The carbonyl ligand engages in a range of bonding modes in metal carbonyl dimers and clusters. In the most common bridging mode, the CO ligand bridges a pair of metals. This bonding mode is observed in the commonly available metal carbonyls: Co2(CO)8, Fe2(CO)9, Fe3(CO)12, and Co4(CO)12. In certain higher nuclearity clusters, CO bridges between three or even four metals. These ligands are denoted μ3-CO and μ4-CO. Less common are bonding modes in which both C and O bond to the metal, e.g. μ3-η2.
Infrared spectroscopy is a sensitive probe for the presence of bridging carbonyl ligands. For compounds with doubly bridging CO ligands, denoted μ2-CO or often just μ-CO, νCO, νCO is usually shifted by 100–200 cm−1 to lower energy compared to the signatures of terminal CO, i.e. in the region 1800 cm−1. Bands for face capping (μ3) CO ligands appear at even lower energies. Typical values for rhodium cluster carbonyls are: In addition to symmetrical bridging modes, CO can be found bridge unsymmetrically or through donation from a metal d orbital to the π* orbital of CO, The increased π-bonding due to back-donation from multiple metal centers results in further weakening of the C-O bond.
Most mononuclear carbonyl complexes are colorless or pale yellow volatile liquids or solids that are flammable and toxic. Vanadium hexacarbonyl, a uniquely stable 17-electron metal carbonyl, is a blue-black solid. Di- and polymetallic carbonyls tend to be more deeply colored. Triiron dodecacarbonyl (Fe3(CO)12) forms deep green crystals. The crystalline metal carbonyls often are sublimable in vacuum, although this process is often accompanied by degradation. Metal carbonyls are soluble in nonpolar and polar organic solvents such as benzene, diethyl ether, acetone, glacial acetic acid and carbon tetrachloride. Some salts of cationic and anionic metal carbonyls are soluble in water or lower alcohols.
Important analytical techniques for the characterization of metal carbonyls are infrared spectroscopy and 13C NMR spectroscopy. These two techniques provide structural information on two very different time scales. Infrared active vibrational modes, such as CO-stretching vibrations are often fast compared to intramolecular processes, whereas NMR transitions occur at lower frequencies and thus sample structures on a time scale that, it turns out, is comparable to the rate of intramolecular ligand exchange processes. NMR data provides information on "time-averaged structures," whereas IR is an instant "snapshot." Illustrative of the differing time scales, investigation of dicobalt octacarbonyl (Co2(CO)8) by means of infrared spectroscopy provides 13 νCO bands, far more than expected for a single compound. This complexity reflects the presence of isomers with and without bridging CO-ligands. The 13C-NMR spectrum of the same substance exhibits only a single signal at a chemical shift of 204 ppm. This simplicity indicates that the isomers quickly interconvert.
Iron pentacarbonyl exhibits only a single 13C-NMR signal owing to rapid exchange of the axial and equatorial CO ligands by Berry pseudorotation.
The most important technique for characterizing metal carbonyls is infra-red spectroscopy. The C-O vibration, typically denoted νCO, occurs at 2143 cm−1 for CO gas. The energies of the νCO band for the metal carbonyls correlates with the strength of the carbon-oxygen bond, and inversely correlated with the strength of the π-backbonding between the metal and the carbon. The π basicity of the metal center depends on a lot of factors; in the isoelectronic series (Ti to Fe) at the bottom of this section, the hexacarbonyls show decreasing π-backbonding as one increases (makes more positive) the charge on the metal. π-Basic ligands increase π-electron density at the metal, and improved backbonding reduces νCO. The Tolman electronic parameter uses the Ni(CO)3 fragment to order ligands by their π-donating abilities.
The number of vibrational modes of a metal carbonyl complex can be determined by group theory. Only vibrational modes that transform as the electric dipole operator will have non-zero direct products and are observed. The number of observable IR transitions (but not the energies) can thus be predicted. For example, the CO ligands of octahedral complexes, e.g. Cr(CO)6, transform as a1g, eg, and t1u, but only the t1u mode (anti-symmetric stretch of the apical carbonyl ligands) is IR-allowed. Thus, only a single νCO band is observed in the IR spectra of the octahedral metal hexacarbonyls. Spectra for complexes of lower symmetry are more complex. For example, the IR spectrum of Fe2(CO)9 displays CO bands at 2082, 2019, 1829 cm−1. The number of IR-observable vibrational modes for some metal carbonyls are shown in the table. Exhaustive tabulations are available.
|carbonyl||νCO, µ1 (cm−1)||νCO, µ2 (cm−1)||νCO, µ3 (cm−1)|
|Rh2(CO)8||2060, 2084||1846, 1862|
|Rh4(CO)12||2044, 2070, 2074||1886|
The traditional method for the study of metal carbonyls is the 13C NMR spectroscopy. To improve the sensitivity of this technique, complexes are often enriched 13CO. Typical range for the chemical shift for terminally bound ligands is 150 to 220 ppm. Bridging ligands absorb between 230 to 280 ppm. The 13C signals shift toward higher fields with an increasing atomic number of the central metal.
The nuclear magnetic resonance spectroscopy can be used for experimental determination of the complex dynamics. The activation energy of ligand exchanges processes can be determined by the temperature dependence of the line broadening.
Mass spectrometry provides information about the structure and composition of the complexes. Spectra for metal polycarbonyls are often easily interpretable, because the dominant fragmentation process is the loss of carbonyl ligands (m/z = 28).
Electron impact ionization is the most common technique for characterizing the neutral metal carbonyls. Neutral metal carbonyls can be converted to charged species by derivatization, which enables the use of electrospray ionization, instrumentation for which is often widely available. For example, treatment of a metal carbonyl with alkoxide generates an anionic metallaformate that is amenable for ESI-MS:
Metal carbonyls react with azide to give isocyanato complexes with release of nitrogen. By adjusting the cone voltage and/or temperature, the degree of fragmentation can be controlled. The molar mass of the parent complex can be determined, as well as information about structural rearrangements involving loss of carbonyl ligands under ESI-MS conditions.
In the investigation of the infrared spectrum of the Galactic Center monoxide vibrations of iron carbonyls in interstellar dust clouds were detected. Iron carbonyl clusters were also observed in Jiange H5 chondrites identified by infrared spectroscopy. Four infrared stretching frequencies were found for the terminal and bridging carbon monoxide ligands.
In the oxygen-rich atmosphere of earth metal carbonyls are subject to oxidation to the metal oxides. It is discussed whether in the reducing hydrothermal environments of the pre-biotic prehistory such complexes were formed and could have been available as catalysts for the synthesis of critical biochemical compounds such as pyruvic acid. Traces of the carbonyls of iron, nickel, and tungsten were found in the gaseous emanations from the sewage sludge of municipal treatment plants.
The hydrogenase enzymes contain CO bound to iron. Apparently the CO stabilizes low oxidation states, which facilitates the binding of hydrogen. The enzymes carbon monoxide dehydrogenase and acetyl coA synthase also are involved in bio-processing of CO. Carbon monoxide containing complexes are invoked for the toxicity of CO and signaling.
The synthesis of metal carbonyls is subject of intense organometallic research. Since the work of Mond and then Hieber, a lotof procedures have been developed for the preparation of mononuclear metal carbonyls as well as homo-and hetero-metallic carbonyl clusters.
Nickel tetracarbonyl and iron pentacarbonyl can be prepared according to the following equations by reaction of finely divided metal with carbon monoxide:
Nickel carbonyl is formed with carbon monoxide already at 80 °C and atmospheric pressure, finely divided iron reacts at temperatures between 150 and 200 °C and a carbon monoxide pressure of 50 to 200 bar. Other metal carbonyls are prepared by less direct methods.
Some metal carbonyls are prepared by the reduction of metal halides in the presence of high pressures of carbon monoxide under pressure. A variety of reducing agents are employed, including copper, aluminum, hydrogen, as well as metal alkyls such as triethylaluminum. Illustrative is the formation of chromium hexacarbonyl from anhydrous chromium(III) chloride in benzene with aluminum as a reducing agent, and aluminum chloride as the catalyst:
Tungsten, molybdenum, manganese, and rhodium salts may be reduced with lithium aluminum hydride. Vanadium hexacarbonyl is prepared with sodium as a reducing agent in chelating solvents such as diglyme.
In aqueous phase nickel or cobalt salts can be reduced, for example, by sodium dithionite. In the presence of carbon monoxide, cobalt salts are quantitatively converted to the tetracarbonylcobalt(-1) anion:
If metal oxides are used carbon dioxide is formed as a reaction product. In the reduction of metal chlorides with carbon monoxide phosgene is formed, as in the preparation of osmium carbonyl chloride from the chloride salts. Carbon monoxide is also suitable for the reduction of sulfides, where carbonyl sulfide is the byproduct.
Photolysis or thermolysis of mononuclear carbonyls generates bi- and multimetallic carbonyls such as diiron nonacarbonyl (Fe2(CO)9). On further heating, the products decompose eventually into the metal and carbon monoxide.
The thermal decomposition of triosmium dodecacarbonyl (Os3(CO)12) provides higher-nuclear osmium carbonyl clusters such as Os4(CO)13, Os6(CO)18 up to Os8(CO)23.
Mixed ligand carbonyls of ruthenium, osmium, rhodium, and iridium are often generated by abstraction of CO from solvents such as dimethylformamide (DMF) and 2-methoxyethanol. Typical is the synthesis of IrCl(CO)(PPh3)2 from the reaction of iridium(III) chloride and triphenylphosphine in boiling DMF solution.
The synthesis of ionic carbonyl complexes is possible by oxidation or reduction of the neutral complexes. Anionic metal carbonylates can be obtained for example by reduction of dinuclear complexes with sodium. A familiar example is the sodium salt of iron tetracarbonylate (Na2Fe(CO)4,Collman's reagent), which is used in organic synthesis.
The cationic hexacarbonyl salts of manganese, technetium and rhenium can be prepared from the carbonyl halides under carbon monoxide pressure by reaction with a Lewis acid.
The use of strong acids succeeded in preparing gold carbonyl cations such as [Au(CO)2]+, which is used as a catalyst for the carbonylation of olefins. The cationic platinum carbonyl complex [Pt(CO)4]+ can be prepared by working in so-called super acids such as antimony pentafluoride.
Metal carbonyls are important precursors for the synthesis of other organometalic complexes. The main reactions are the substitution of carbon monoxide by other ligands, the oxidation or reduction reactions of the metal center and reactions of carbon monoxide ligand.
The substitution of CO ligands can be induced thermally or photochemically by donor ligands. The range of ligands is large, and includes phosphines, cyanide (CN-), nitrogen donors, and even ethers, especially chelating ones. Olefins, especially diolefins, are effective ligands that afford synthetically useful derivatives. Substitution of 18-electron complexes generally follows a dissociative mechanism, involving 16-electron intermediates.
Substitution proceeds via a dissociative mechanism:
Substitution in 17-electron complexes, which are rare, proceeds via associative mechanisms with a 19-electron intermediates.
The rate of substitution in 18-electron complexes is sometimes catalysed by catalytic amounts of oxidants, via electron-transfer.
For iron pentacarbonyl, one obtains the tetracarbonylferrate with loss of CO:
Mercury can insert into the metal-metal bonds of some polynuclear metal carbonyls:
The CO ligand is often susceptible to attack by nucleophiles. For example, trimethylamine oxide and bistrimethylsilylamide convert CO ligands to CO2 and CN-, respectively. In the "Hieber base reaction", hydroxide ion attacks the CO ligand to give a metallacarboxylic acid, followed by the release of carbon dioxide and the formation of metal hydrides or carbonylmetalates. A well-known example of this nucleophilic addition reaction is the conversion of iron pentacarbonyl to hydridorion tetracarbonyl anion:
Protonation of the hydrido anion gives the neutral iron tetracarbonyl hydride:
Despite being in low formal oxidation states, metal carbonyls are relatively unreactive toward many electrophiles. For example, they resist attack by alkylating agents, mild acids, mild oxidizing agents. Most metal carbonyls do undergo halogenation. Iron pentacarbonyl, for example, forms ferrous carbonyl halides:
Metal-metal bonds are cleaved by halogens:
Most metal carbonyl complexes contain a mixture of ligands. Examples include the historically important IrCl(CO)(P(C6H5)3)2 and the anti-knock agent (CH3C5H4)Mn(CO)3. The parent compounds for many of these mixed ligand complexes are the binary carbonyls, i.e. species of the formula [Mx(CO)n]z, many of which are commercially available. The formula of many metal carbonyls can be inferred from the 18 electron rule.
Large anionic clusters of Ni, Pd, and Pt are also well known.
|Metal Carbonyl hydride||pKa|
Metal carbonyls are relatively distinctive in forming complexes with negative oxidation states. Examples include the anions discussed above. These anions can be protonated to give the corresponding metal carbonyl hydrides. The neutral metal carbonyl hydrides are often volatile and can be quite acidic.
Metal carbonyls are used in several industrial processes. Perhaps the earliest application was the extraction and purification of nickel via nickel tetracarbonyl by the Mond process (see also carbonyl metallurgy).
By a similar process carbonyl iron, a highly pure metal powder, is prepared by thermal decomposition of iron pentacarbonyl. Carbonyl iron is used inter alia for the preparation of inductors, pigments, as dietary supplements, in the production of radar-absorbing materials in the stealth technology, and in Thermal spraying.
Metal carbonyls are used in a number of industrially important carbonylation reactions. In the oxo process, an olefin, dihydrogen, and carbon monoxide react together with a catalyst (e.g. dicobalt octacarbonyl to give aldehydes. Illustrative is the production of butyraldehyde:
Butyraldehyde is converted on an industrial scale to 2-Ethylhexanol, a precursor to PVC plasticizers, by aldol condensation, followed by hydrogenation of the resulting hydroxyaldehyde. The "oxo aldehydes" resulting from hydroformylation are used for large-scale synthesis of fatty alcohols, which are precursors to detergents. The hydroformylation is a reaction with high atom economy, especially if the reaction proceeds with high regioselectivity.
Another important reaction catalyzed by metal carbonyls is the hydrocarboxylation. The example below is for the synthesis of acrylic acid and acrylic acid esters:
Also the cyclization of acetylene to cyclooctatetraene uses metal carbonyl catalysts:
In the Monsanto and Cativa processes, acetic acid is produced from methanol, carbon monoxide, and water using hydrogen iodide as well as rhodium and iridium carbonyl catalysts, respectively. Related carbonylation reactions afford acetic anhydride.
Many ligands are known to form homoleptic and mixed ligand complexes that are analogous to the metal carbonyls.
Metal nitrosyls, featuring NO as a ligand are numerous, although homoleptic derivatives are not. Relative to CO, NO is a stronger acceptor and isocyanides are better donors. Well known nitrosyl carbonyls include CoNO(CO)3 and Fe(NO)2(CO)2.
Complexes containing CS are known but are uncommon. The rarity of such complexes is attributable in part to the fact that the obvious source material, carbon monosulfide, is unstable. Thus, the synthesis of thiocarbonyl complexes requires more elaborate routes, such as the reaction of disodium tetracarbonylferrate with thiophosgene:
Complexes of CSe and CTe are very rare.
All metal carbonyls undergo substitution by organophosphorus ligands. For example, the series Fe(CO)5-x(PR3)x is well known for various phosphine ligands for x = 1, 2, and 3. PF3 behaves similarly but is remarkable because it readily forms homoleptic analogues of the binary metal carbonyls. For example the volatile, stable complexes Fe(PF3)5 and Co2(PF3)8 represent CO-free analogues of Fe(CO)5 and Co2(CO)8 (unbridged isomer).
Isocyanides also form extensive families of complexes that are related to the metal carbonyls. Typical isocyanide ligands are methyl and t-butyl isocyanides (Me3CNC). A special case is CF3NC, an unstable molecule that forms stable complexes whose behavior closely parallels that of the metal carbonyls.
The toxicity of metal carbonyls is due to toxicity of carbon monoxide, the metal, and because of the volatility and instability of the complexes. Exposure occurs by inhalation, or for liquid metal carbonyls by ingestion or due to the good fat solubility by skin resorption. Most clinical experience were gained from toxicological poisoning with nickel carbonyl and iron pentacarbonyl. Nickel carbonyl is considered as one of the strongest inhalation poisons.
Inhalation of nickel carbonyl causes acute non-specific symptoms similar to a carbon monoxide poisoning as nausea, cough, headaches, fever and dizziness. After some time, severe pulmonary symptoms such as cough, tachycardia cyanosis or problems in the gastrointestinal tract occur. In addition to pathological alterations of the lung, such as by metallation of the alveoli, damages are observed in the brain, liver, kidneys, adrenal glands and the spleen. A metal carbonyl poisoning often requires a long-lasting recovery.
Chronic exposure by inhalation of low concentrations of nickel carbonyl can cause neurological symptoms such as insomnia, headaches, dizziness and memory loss. Nickel carbonyl is considered carcinogenic, but it can take 20 to 30 years from the start of exposure to the clinical manifestation of cancer.
Initial experiments on the reaction of carbon monoxide with metals were carried out by Justus von Liebig in 1834. By passing carbon monoxide over molten potassium he prepared a substance having the empirical formula KCO, which he called Kohlenoxidkalium. As demonstrated later, the compound was not a metal carbonyl, but the potassium salt of ´hexahydroxy benzene and the potassium salt of dihydroxy acetylene
The synthesis of the first true heteroleptic metal carbonyl complex was performed by Paul Schützenberger in 1868 by passing chlorine and carbon monoxide over platinum black, where dicarbonyldichloroplatinum (Pt(CO)2Cl2) was formed.
Ludwig Mond, one of the founders of Imperial Chemical Industries, investigated in the 1890s with Carl Langer and Friedrich Quincke various processes for the recovery of chlorine which was lost in the Solvay process by nickel metals, oxides and salts. As part of their experiments the group treated nickel with carbon monoxide. They found that the resulting gas colored the gas flame of a burner in a greenish-yellowish color; when heated in a glass tube it formed a nickel mirror. The gas could be condensed to a colorless, water-clear liquid with a boiling point of 43 °C. Thus, Mond and his coworker had discovered the first pure, homoleptic metal carbonyl, nickel tetracarbonyl (Ni(CO)4). The unusual high volatility of the metal compound nickel tetracarbonyl led Kelvin with the statement that Mond had "given wings to the metals'.
The following year, Mond and Marcellin Berthelot independently discovered iron pentacarbonyl, which is produced by a similar procedure as nickel tetracarbonyl. Mond recognized the economic potential of this class of compounds, which he commercially used in the Mond process and financed more research on related compounds. Heinrich Hirtz and his colleague M. Dalton Cowap synthesized metal carbonyls of cobalt, molybdenum, ruthenium, and diiron nonacarbonyl. In 1906 James Dewar and H. O. Jones were able to determine the structure of Diiron nonacarbonyl, which is produced from iron pentacarbonyl by the action of sunlight. After Mond, who died in 1909, the chemistry of metal carbonyls fell for several years in oblivion. The BASF started in 1924 the industrial production of iron pentacarbonyl by a process which was developed by Alwin Mittasch. The iron pentacarbonyl was used for the production of high-purity iron, so-called carbonyl iron, and iron oxide pigment. Not until 1927 did A. Job and A. Cassal succeed in the preparation of chromium hexacarbonyl and tungsten hexacarbonyl, the first synthesis of other homoleptic metal carbonyls.
Walter Hieber played in the years following 1928 a decisive role in the development of metal carbonyl chemistry. He systematically investigated and discovered, among other things, the Hieber base reaction, the first known route to Metal carbonyl hydrides and synthetic pathways leading to metal carbonyls such as dirhenium decacarbonyl. Hieber, who was since 1934 the Director of the Institute of Inorganic Chemistry at the Technical University Munich published in four decades 249 papers on metal carbonyl chemistry.
Also in the 1930s Walter Reppe, an industrial chemist and later board member of the BASF, discovered a number of homogeneous catalytic processes, such as the hydrocarboxylation, in which olefins or alkynes react with carbon monoxide and water to form products such as unsaturated acids and their derivatives. In these reactions, for example, nickel carbonyl or cobalt carbonyls act as catalysts. Reppe also discovered the cyclotrimerization and tetramerization of acetylene and its derivatives to benzene and benzene derivatives with metal carbonyls as catalysts. BASF built in the 1960s a production facility for acrylic acid by the Reppe process, which was only superseded in 1996 by more modern methods based on the catalytic propylene oxidation.
For the rational design of new complexes the concept of the isolobal analogy has been found useful. Roald Hoffmann was awarded with the Nobel Prize in chemistry for the development of the concept. The concept describes metal carbonyl fragments of M(CO)n as parts of octahedral building blocks in analogy to the tetrahedral CH3-, CH2- or CH- fragments in organic chemistry. In example Dimanganese decacarbonyl is formed in terms of the isolobal analogy of two d7Mn(CO)5 fragments, that are isolobal to the methyl radical CH3•. These can in analogy to the combination of methyl radicals to Ethane combine to Dimanganese decacarbonyl. The presence of isolobal analog fragments does not mean that the desired structures can be synthezied. In his Nobel Prize lecture Hoffmann emphasized that the isolobal analogy is a useful but simple model, and in some cases does not lead to success.
The economic benefits of metal-catalysed carbonylations, e.g. Reppe chemistry and hydroformylation, led to growth of the area. Metal carbonyl compounds were discovered in the active sites of three naturally occurring enzymes.
|Wikimedia Commons has media related to: Metal carbonyls|