Organometallic chemistry

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n-Butyllithium, an organometallic compound.

Organometallic chemistry is the study of chemical compounds containing bonds between carbon and a metal.[1][2] 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 and Grignard reagents which contain lithium and copper, and magnesium respectively. Tetracarbonyl nickel, and ferrocene are examples of organometallic compounds containing transition metals.

In addition to the traditional metals and semimetals, elements such as boron, silicon, arsenic, and selenium are considered to form organometallic compounds. Examples include organomagnesium compounds such as iodo(methyl)magnesium MeMgI, diethylmagnesium (Et2Mg); organolithium compounds such as butyllithium (BuLi), organozinc compounds such as chloro(ethoxycarbonylmethyl)zinc (ClZnCH2C(=O)OEt); organocopper compounds such as lithium dimethylcuprate (Li+[CuMe2]); and organoborane compounds such as triethylborane (Et3B).

Organic coordination compounds

Organic coordination compounds are complexes with coordination bond between the metal and the organic molecule. The metal can be coordinated to a heteroatom such as oxygen or nitrogen, or to an organic residue such as a benzene ring or a carbon-carbon double bond.

Many organic coordination compounds exist in biological systems. For example, hemoglobin and myoglobin contain an iron center coordinated to the nitrogens of a porphyrin ring; magnesium is the center of a chlorin ring in chlorophyll. The specialized 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 only a few known in biology. With the help of the MTR enzyme, it transfers 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

Organometallic compounds find practical use in 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. 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 catalyst is the Grubbs catalyst, a carbenoid (an organometallic compound of a carbene and a metal).

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

  1. Robert H. Crabtree (2005). The Organometallic Chemistry of the Transition Metals. Wiley. p. 560. ISBN 978-0-471-66256-3. 
  2. Toreki, R. (2003-11-20). "Organometallics Defined". Interactive Learning Paradigms Incorporated. 

External links

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ca:Compost organometàl·lic cs:Organokovová chemie de:Organometallchemieko:유기금속화학 id:Kimia organologam it:Chimica metallorganica he:כימיה אורגנומתכתית la:Chemia Organometallica lb:Organometallchimie lt:Organometaliniai junginiai hu:Fémorganikus kémia mk:Органометално соединение nl:Organometaalchemiesimple:Organometallic compound su:Kimia organologam th:ออร์แกนโนเมทัลลิกเคมีuk:Металоорганічні сполуки


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