The use of organometallic reagents in organic synthesis had its beginning around with the work of Victor Grignard, who discovered that alkyl and aryl. Ch Organometallic Compounds. Compounds that contain a metal-carbon bond, R-M, are known as "organometallic" compounds. Organometallic compounds of Li, Mg (Grignard reagents) are amongst some of the most important organic reagents. Many other metals have been utilised, for example Na, Cu and Zn. Sigma-Aldrich offers a diverse range of organometallic reagents that participate in cross-coupling reactions and facilitate the discovery of new bond forming.


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Structure and properties[ edit ] The metal-carbon bond in organometallic compounds is generally highly covalent.

Organometallic Reagents in Synthesis

For highly electropositive elements, such as lithium and sodium, the carbon ligand exhibits carbanionic character, but free carbon-based anions are extremely organometallic reagents, an example being cyanide.

Concepts and techniques[ edit ] As in other areas of chemistry, electron counting is useful for organizing organometallic organometallic reagents. The 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.

Organometallic chemistry

As well as X-ray diffraction, NMR and infrared spectroscopy are common organometallic reagents 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: Organometallic reagents Organometallic Reagents Reaction of Organometallic Reagents with Various Carbonyls Because organometallic reagents react as their corresponding carbanion, they are excellent nucleophiles.

The basic reaction involves the nucleophilic attack of the carbanionic carbon in the organometallic reagent with the electrophilic carbon in the carbonyl to form alcohols.

Both Grignard and Organolithium Reagents will perform these reactions. Going organometallic reagents Reactants to Products Simplified Mechanism for the Addition to Carbonyls The mechanism for a Grignard agent is shown; the mechanism for an organometallic reagent is the same.

Although not usually done with Grignard reagents, organolithium reagents can be used as strong bases.


Both Grignard reagents and organolithium reagents react with water to form the corresponding hydrocarbon. This is why so much care is needed to insure dry glassware and solvents when working with organometallic reagents. In fact, the reactivity of Grignard reagents and organolithium reagents can be exploited to create a new method for the conversion of halogens to the corresponding hydrocarbon illustrated below.

The halogen is converted to an organometallic reagents reagent and then subsequently reacted with water to from an alkane. Limitation of Organometallic Reagents As discussed above, Grignard and organolithium reagents are powerful bases.

Organometallic chemistry - Wikipedia

In organometallic reagents, it is useful to think about Grignard reagents and organolithium reagents as sources of negatively charged carbon atoms, i. Since carbon is not a very electronegative element, it is very reactive when it bears a negative charge.

Organometallic Reagents as Bases In order to appreciate just how reactive carbanions are, consider the series of anions and their conjugate acids shown in Figure 1. Ignoring for the moment the different ways in which chemists write methane and ammonia on the one hand and water and hydrogen fluoride on the other wierd, huh?

Furthermore, the pKa scale is logarithmic or exponential. Thus, hydrogen fluoride is times more acidic than water.

Similarly, water is more acidic than ammonia. Knowing the relative acidities of the compounds in Figure 1 means you also know their relative basicities: Clearly then, methane is the weakest acid of organometallic reagents four conjugate acids shown in Figure 1, while the methide anion is the strongest base, and, by extension, the best nucleophile.

The trend in base strength exhibited by the four anions in Figure 1 is attributed to the difference in nuclear charge of the central atom in each ion. Carbon has 6 protons attracting the lone pair organometallic reagents electrons, nitrogen has 7, oxygen 8, and fluorine 9.

Preparation Because they are so reactive, organometallic reagents are generally prepared just before use.

8.7: Organometallic Reagents: Sources of Nucleophilic Carbon for Alcohol Synthesis

Organolithium reagents organometallic reagents available commercially as solutions in inert solvents such as diethyl ether, tetrahydrofuran THFor pentane. Still, they have a short shelf life and must be handled under an inert atmosphere.


The procedure for generating either type of reagent is organometallic reagents Equations 1 and 2 depict the preparation of phenyl magnesium bromide and methyl lithium, respectively.

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