organometallic chemistry

organometallic chemistry

organometallic chemistry, the reactions and use of a class of compounds (R-M) that contain a covalent bond between carbon and metal. They are prepared either by direct reaction of the metal with an organic compound or by replacement of a metal from another organometallic substance. Their use is based on the polar R-M bond, in which the carbon atom carries a partial negative charge, and on the nature of the metal atom. In synthesis they act as nucleophiles that can bond with relatively positive carbon atoms in compounds such as alkyl halides, aldehydes, and ketones. For example, the Grignard reagent, RMgX (where X equals Br, Cl, or I), and organolithium compounds react with ketones to give secondary alcohols. In industry, butyllithium is used for the polymerization of isoprene in the manufacture of synthetic rubber; metalloorganic compounds serve as catalysts. The semimetals, boron, and silicon are important organometallics; organoboranes are used in synthesis, while organosilicones are polymerized to manufacture plastics and elastomers. Many organometallics are toxic primarily because of the toxicity of the metal. For example tetraethyl lead has been banned as gasoline additive and the conversion of mercury to mercury alkyls by fish has had serious consequences in Japan.

Organometallic chemistry is the study of chemical compounds containing bonds between carbon and a metal. Since many compounds without such bonds are chemically similar, an alternative may be compounds containing metal-element bonds of a largely covalent character. Organometallic chemistry combines aspects of inorganic chemistry and organic chemistry.

Organometallic compounds

Organometallic compounds are also known as organo-inorganics, metallo-organics and metalorganics. Organometallic compounds are distinguished by the prefix "organo-" e.g. organopalladium compounds. Examples of such organometallic compounds include all Gilman which contain lithium and copper. Tetracarbonyl nickel, and ferrocene are examples of organometallic compounds containing transition metals. Other examples include organomagnesium compounds like iodo(methyl)magnesium MeMgI, diethylmagnesium (Et2Mg), and all Grignard reagents; organolithium compounds such as butyllithium (BuLi), organozinc compounds such as chloro(ethoxycarbonylmethyl)zinc (ClZnCH2C(=O)OEt); and organocopper compounds such as lithium dimethylcuprate (Li+[CuMe2]).

In addition to the traditional metals, lanthanides, actinides, and semimetals, elements such as boron, silicon, arsenic, and selenium are considered to form organometallic compounds, e.g. organoborane compounds such as triethylborane (Et3B).

Coordination compounds with organic ligands

Many complexes feature coordination bonds between a metal and organic ligands. The organic ligands often bind the metal through a heteroatom such as oxygen or nitrogen, in which case such compounds are considered coordination compounds. However, if any of the ligands form a direct M-C bond, then complex is usually considered to be organometallic, e.g., [(C6H6)Ru(H2O)3]2+. Furthermore, many lipophilic compounds such as metal acetylacetonates and metal alkoxides are called "metalorganics."

Many organic coordination compounds occur naturally. For example, hemoglobin and myoglobin contain an iron center coordinated to the nitrogen atoms of a porphyrin ring; magnesium is the center of a chlorin ring in chlorophyll. The field of such inorganic compounds is known as bioinorganic chemistry. In contrast to these coordination compounds, methylcobalamin (a form of Vitamin B12), with a cobalt-methyl bond, is a true organometallic complex, one of the few known in biology. This subset of complexes are often discussed within the subfield of bioorganometallic chemistry. Illustrative of the many functions of the B12-dependent enzymes, the MTR enzyme catalyzes the transfer of a methyl group from a nitrogen on N5-methyl-tetrahydrofolate to the sulfur of homocysteine to produce methionine.

Structure and properties

The status of compounds in which the canonical anion has a delocalized structure in which the negative charge is shared with an atom more electronegative than carbon, as in enolates, may vary with the nature of the anionic moiety, the metal ion, and possibly the medium; in the absence of direct structural evidence for a carbon–metal bond, such compounds are not considered to be organometallic.

Depending mostly on the nature of metallic ion and somewhat on the nature of the organic compound, the character of the bond may either be ionic or covalent. Organic compounds bonded to sodium or potassium are primarily ionic. Those bonded to lead, tin, mercury, etc. are considered to have covalent bonds, and those bonded to magnesium or lithium have bonds with intermediate properties.

Organometallic compounds with bonds that have characters in between ionic and covalent are very important in industry, as they are both relatively stable in solutions and relatively ionic to undergo reactions. Two important classes are organolithium and Grignard reagents. In certain organometallic compounds such as ferrocene or dibenzenechromium, the pi orbitals of the organic moiety ligate the metal.

Applications

Organometallics find practical uses as stoichiometric and catalytically active compounds. Tetraethyl lead previously was combined with gasoline as an antiknock agent. Due to lead's toxicity it is no longer used, its replacements being other organometallic compounds such as ferrocene and methylcyclopentadienyl manganese tricarbonyl (MMT). The Monsanto process utilizes a rhodium-carbonyl complex to manufacture acetic acid from methanol and carbon monoxide industrially. Similarly, the Wacker process is used in the oxidation of Olefins. The Ziegler-Natta catalyst is a titanium-based organometallic compound used in the production of polyethylene and other polymers.

Ryoji Noyori's chiral ruthenium-BINAP complex catalytically reduces beta-ketoesters to secondary alcohols in the production of fine chemicals and pharmaceuticals. Another common industrial organometallic compound is the Grubbs catalyst, a carbenoid (an organometallic compound of a carbene and a metal).

Organometallic compounds of the reactive metals such as lithium or zinc are extremely basic and may also act as reductants. These superbases are used in organic syntheses. Butyllithium is an example, widely used in synthetic organic chemistry. They are air-sensitive, however, and their flammability severely limits their industrial use.

Concepts

Electron counting is key in understanding organometallic chemistry. The 18-electron rule is helpful in predicting the stabilities of organometallic compounds. Organometallic compounds which have 18 electrons (filled s, p, and penultimate d orbitals) are relatively stable. This suggests the compound is isolable, but it can result in the compound being inert.

To understand chemical bonding and reactivity in organometallic compounds the isolobal principle should be used. NMR and infrared spectroscopy are common techniques used to determine structure and bonding in this field. Scientists are allowed to probe fluxional behaviors of compounds with variable-temperature NMR.

Organometallic compounds undergo several important reactions:

History

Early developments in organometallic chemistry include Louis Claude Cadet’s synthesis of methyl arsenic compounds related to cacodyl, William Christopher Zeise's platinum-ethylene complex, Edward Frankland’s discovery of dimethyl zinc, Ludwig Mond’s discovery of Ni(CO)4, and Victor Grignard’s organomagnesium compounds. The abundant and diverse products from coal and petroleum led to Ziegler-Natta, Fischer-Tropsch, hydroformylation catalysis which employ CO, H2, and alkenes as feedstocks and ligands.

Recognition of organometallic chemistry as a distinct subfield culminated in the Nobel Prizes to Ernst Fischer and Geoffrey Wilkinson for work on metallocenes. In 2005, Yves Chauvin, Robert H. Grubbs and Richard R. Schrock shared the Nobel Prize for metal-catalyzed olefin metathesis.

Organometallic chemistry timeline

Organometallics

See also

References

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