Organozinc Compounds

Organozinc Compounds

 

metallo-organic compounds containing a zinc-carbon bond. There are both complete organozinc compounds, R2Zn, and mixed organozinc compounds, RZnX, where the R are identical or different hydrocarbon radicals, for example, CH3, C2H5, CH2=CH, or C6H5, and X is an acid residue, most often, Br or I.

Organozinc compounds were first synthesized by E. Frankland in 1849 in the reaction of zinc with alkyl iodides: Zn + RI → RZnI. The mixed organozinc compounds formed are symmetrized upon heating: 2RZnI→ R2Zn + Znl2. This method is still important today. Another method for the synthesis of organozinc compounds is the alkylation of zinc chloride by reactive metalloorganic compounds of lithium, magnesium, and aluminum: 2RMgX + ZnCl2 → R2Zn + 2MgClX. A third method involves the reaction of zinc with dialkylmercury or arylmercury: Zn + R2Hg → R2Zn + Hg.

Organic compounds are either liquids, such as diethylzinc, (C2H5)2Zn, with a boiling point of 116.8°C, or solids, such as diphenylzinc, (C6H5)2Zn, with a melting point of 107°C. They are unstable in the presence of air, so much so that the lower members of the R2Zn series (up to R = C5H11) ignite spontaneously. They are vigorously decomposed by water. Thus, their reactions are carried out in an inert atmosphere of nitrogen, argon, or carbon dioxide. The chemical properties of organozinc compounds are similar to those of other metallo-organic compounds of the transition metals, although organozinc compounds are less reactive than organolithium and organomagnesium compounds. Therefore, organozinc compounds are used in the synthesis of ketones, ketoethers, and hydrocarbons with a quarternary carbon atom. Organozinc compounds form donor-acceptor complexes with dioxane, ether, and olefinic oxides, for example, ZnR2· C4H8O2 and RZnX· O(C2H5)2; with alkyl and hydride compounds of alkali and alkaline-earth metals, they form saltlike complexes, for example, MeZnR3, Me2ZnR4, and MeZnR2H, where Me is an alkali metal.

The Kazan school of Russian chemists, headed by A. M. Butlerov, made important contributions to the development of the chemistry of organozinc compounds (see, for example, ZAITSEV REACTION). Organozinc compounds are intermediate products in the production of β-hydroxy carboxylic acids (seeREFORMATSKY REACTION) and cyclopropane hydrocarbons. They are used as catalysts for the polymerization of olefinic oxides and carbonyl compounds. However, organozinc compounds are of little industrial significance.

REFERENCE

Sheverdina, N. I., and K. A. Kocheshkov. Tsink, kadmii. Moscow, 1944.

V. V. GAVRILENKO

References in periodicals archive ?
Among the topics are structural chemistry, thermochemistry, the mass spectrometry of organozinc compounds, and the rearrangements and dynamic behavior of organozinc derivatives.
Seebach discussed the catalytic use of similar complexes derived from tetraaryl dioxolane dimethanols (TADDOLs) and tetraisopropoxy titanium to mediate asymmetric addition of organozinc compounds to compounds such as saturated and unsaturates aldehydes.