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Organometallic chemistry

, an organometallic compound. Four lithium atoms (in purple) form a tetrahedron, with four butyl groups attached to the faces (carbon is black, hydrogen is white).]] Organometallic chemistry is the study of chemical compounds containing at least one chemical bond between a carbon atom of an organic compound and a metal, including alkaline, alkaline earth, transition metal, and other cases. Moreover, some related compounds such as transition metal hydrides and metal phosphine complexes are often included in discussions of organometallic compounds. The field of organometallic chemistry combines aspects of traditional inorganic and organic chemistry. Organometallic compounds are widely used both stoichiometrically in research and industrial chemical reactions, as well as in the role of catalysts to increase the rates of such reactions (e.g., as in uses of homogeneous catalysis), where target molecules include polymers, pharmaceuticals, and many other types of practical products.

Organometallic compounds

Organometallic compounds are distinguished by the prefix "organo-" e.g. organopalladium compounds. Examples of such organometallic compounds include all Gilman reagents, 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, dimethylmagnesium (Me2Mg), and all Grignard reagents; organolithium compounds such as n-butyllithium (n-BuLi), organozinc compounds such as diethylzinc (Et2Zn) and chloro(ethoxycarbonylmethyl)zinc (ClZnCH2C(=O)OEt); and organocopper compounds such as lithium dimethylcuprate (Li+ CuMe2−). The term " metalorganics" usually refers to metal-containing compounds lacking direct metal-carbon bonds but which contain organic ligands. Metal beta-diketonates, alkoxides, and dialkylamides are representative members of this class. 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). File:Ferrocene.svg| Ferrocene is an archetypal organoiron complex. It is an air-stable, sublimable compound. File:Cobaltocene.svg| Cobaltocene is a structural analogue of ferrocene, but is highly reactive toward air. File:HRh(CO)P3again.png| Tris(triphenylphosphine)rhodium carbonyl hydride is used in the commercial production of many aldehyde-based fragrances. File:Zeise'sSalt.png| Zeise's salt is an example of a transition metal alkene complex. File:Trimethylaluminium-3D-balls.png| Trimethylaluminium is an organometallic compound with a bridging methyl group. It is used in the industrial production of some alcohols File:Dimethylzinc-3D-balls.png| Dimethylzinc has a linear coordination. It is a volatile pyrophoric liquid that is used in the preparation of semiconducting films.

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)32+. Furthermore, many lipophilic compounds such as metal acetylacetonates and metal alkoxides are called "metalorganics." A naturally occurring transition metal alkyl complex is methylcobalamin (a form of Vitamin B12), with a cobalt- methyl bond. This subset of complexes is 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. 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.

Structure and properties

The metal-carbon bond in organometallic compounds is generally highly covalent. For highly electropositive elements, such as lithium and sodium, the carbon ligand exhibits carbanionic character, but free carbon-based anions are extremely rare, an example being cyanide.

Concepts and techniques

As in other areas of chemistry, electron counting is useful for organizing organometallic chemistry. The 18-electron rule is helpful in predicting the stabilities of metal carbonyls and related compounds. Most organometallic compounds do not however follow the 18e rule. Chemical bonding and reactivity in organometallic compounds is often discussed from the perspective of the isolobal principle. As well as X-ray diffraction, NMR and infrared spectroscopy are common techniques used to determine structure. The dynamic properties of organometallic compounds is often probed with variable-temperature NMR and chemical kinetics. Organometallic compounds undergo several important reactions:


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. (Though not always acknowledged as an organometallic compound, Prussian blue, a mixed-valence iron-cyanide complex, was first prepared in 1706 by paint maker Johann Jacob Diesbach as the first coordination polymer and synthetic material containing a metal-carbon bond.) 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


Subspecialty areas of organometallic chemistry include: The following is a presentation of elements of the periodic table with known compounds of carbon with other elements.

Industrial applications

Organometallic compounds find wide use in commercial reactions, both as homogeneous catalysis and as stoichiometric reagents For instance, organolithium, organomagnesium, and organoaluminium compounds, examples of which are highly basic and highly reducing, are useful stoichiometrically, but also catalyze many polymerization reactions. Almost all processes involving carbon monoxide rely on catalysts, notable examples being described as carbonylations. The production of acetic acid from methanol and carbon monoxide is catalyzed via metal carbonyl complexes in the Monsanto process and Cativa process. Most synthetic aldehydes are produced via hydroformylation. The bulk of the synthetic alcohols, at least those larger than ethanol, are produced by hydrogenation of hydroformylation-derived aldehydes. Similarly, the Wacker process is used in the oxidation of ethylene to acetaldehyde. Almost all industrial processes involving alkene-derived polymers rely on organometallic catalysts. The world's polyethylene and polypropylene are produced via both heterogeneously via Ziegler-Natta catalysis and homogeneously, e.g., via constrained geometry catalysts. Most processes involving hydrogen rely on metal-based catalysts. Whereas bulk hydrogenations, e.g. margarine production, rely on heterogeneous catalysts, For the production of fine chemicals, such hydrogenations rely on soluble organometallic complexes or involve organometallic intermediates.Paul N. Rylander, "Hydrogenation and Dehydrogenation" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005. Organometallic complexes allow these hydrogenations to be effected asymmetrically. Many semiconductors are produced from trimethylgallium, trimethylindium, trimethylaluminium, and trimethylantimony. These volatile compounds are decomposed along with ammonia, arsine, phosphine and related hydrides on a heated substrate via metalorganic vapor phase epitaxy (MOVPE) process in the production of light-emitting diodes (LEDs).

Environmental concerns

Natural and contaminant organometallic compounds are found in the environment. Some that are remnants of human use, such as organolead and organomercury compounds, are toxicity hazards. Tetraethyllead was prepared for use as a gasoline additive but has fallen into disuse because of lead's toxicity. Its replacements are other organometallic compounds, such as ferrocene and methylcyclopentadienyl manganese tricarbonyl (MMT). The organoarsenic compound roxarsone is a controversial animal feed additive. In 2006, approximately one million kilograms of it were produced in the U.S alone. is an organoarsenic compound used as an animal feed.]]

See also


Further reading

External links

"green air" © 2007 - Ingo Malchow, Webdesign Neustrelitz
This article based upon the http://en.wikipedia.org/wiki/Organometallic_chemistry, the free encyclopaedia Wikipedia and is licensed under the GNU Free Documentation License.
Further informations available on the list of authors and history: http://en.wikipedia.org/w/index.php?title=Organometallic_chemistry&action=history
presented by: Ingo Malchow, Mirower Bogen 22, 17235 Neustrelitz, Germany