Organometallic compounds of copper

Organometallic compounds of copper were known for a long time before their versatil ity in synthetic organic chemistry was fully appreciated The most useful ones are the lithium dialkylcuprates which result when a copper(I) halide reacts with two equivalents of an alkyllithium in diethyl ether or tetrahydrofuran... 

There are strong similarities between the organometallic compounds of copper and silver. The simple alkyl complexes AgR are thermally unstable. The stability... 

These complexes are obtained by the action of LiPh or MgPh2 on Cul or CuBr. The type of compound formed depends on the Cu Li(Mg) ratio and on the solvent. In the case of methyl compounds, depending on the ratio of CuX(CuMe) to LiMe, various complexes are formed which remain in equilibrium. Gilman s reagent, LiCuMe2, the best known and most commonly utilized organometallic compound of copper, is considerably more complex than can be judged by its stoichiometric composition. 

Organometallic complexes of copper, nickel, and palladium have been used in indole syntheses from arenes. Most of the reactions proceed under relatively mild conditions and in some cases give rise to formation of the less common 2-substituted compounds.68 Good yields of such 2-substituted derivatives are formed in reactions of o-iodoarylamines with cuprous acetylides in dimethylformamide (Scheme 41 ).69 The efficiency of this type of... 

To date, the organometallic chemistry of copper, in terms of isolation and structural characterization of compounds, is essentially limited to the Cu(I) oxidation state. Only a very few examples of other oxidation states are known. The older literature offers a reported synthetic procedure for the synthesis of bis(aryl)copper(II) compounds [33, 34] (see Scheme 1.2), but this result has never been reproduced by others. 

As a consequence of its electronic configuration, a variety of coordination numbers and geometries have been observed for copper(I) compounds, especially for inorganic representatives (see Fig. 1.3) [32]. In the organometallic chemistry of copper, the linear and trigonal coordination geometries in particular, though distorted towards T-shaped, are frequently encountered. 

Por the production of organometallic bodies containing less positive metals than zinc, this method is generally the most convenient, and is of most tmiversal application. Compoimds contmning mercury, tin, lead, antimony, and arsenic have been thus produced but the process has Med when applied to the haloid compounds of copper, silver, platinum, and iron for, although these bodies are violently acted upon, the organic radieala do not unite with the metal... 

Carbonylchlorocopper(I) (A) is a valuable precursor for the synthesis of organometallic and coordination compounds of copper(I). Previous methods11 utilizing water, tetrahydrofuran, methanol, or benzene as solvent may yield lower-purity products because copper(I) chloride is not soluble in these solvents without excess halide ligand. The synthetic method described here also provides a convenient way of growing large crystals of X-ray quality of carbonylchlorocopper(I). 

A. Reactions of Organometallic Compounds with Copper Salts. 217... 

Until recently, the magnesium, lithium, and, to a lesser extent, cadmium compounds were the only organometallic systems of much use in organic synthesis. This situation has changed drastically in the last few years. Compounds of copper have proven to be especially valuable. One of the first examples of these compounds is a reagent prepared from methyllithium and cuprous iodide this reagent is referred to as lithium dimethylcuprate. The reagent adds selectively at the /3-carbon... 

Heaney H, Christie S (2004) Science of synthesis organometallics, compounds of groups 12 and 11, organometallic complexes of copper. Thieme, Stuttgart, pp 305-662 Tom0e CW, Meldal M (2001) Peptidotriazoles copper(I)-catalysed 1,3-dipolar cycloadditions on solid phase. Peptides 2001, Proc. Am. Pept. Symp. American Peptide Society and Kluwer Academic Publishers, San Diego, pp 263-264... 

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