By P. Powell (auth.)
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Additional resources for Principles of Organometallic Chemistry
Example text
Where a strongly polar substituent is present in the unsaturated compound, addition by a polar mechanism can occur. 24 Reactions of diazo compounds 2. 5 Formation of metal-carbon bonds by other insertion reactions The addition of metal hydrides to carbon-carbon double or triple bonds is a special case of a very general reaction type, which involves the addition of a species A-B to an unsaturated system X=Y (or X-Y). -Hal. ). g. ) are described briefly elsewhere (p. 45) as they do not lead to the formation of new M-C bonds.
Much less is known about the structures of the alkyls of heavier alkali metals. That of methylsodium is based on (MeNa) 4 tetramers. MeM(M=K. Rb, Cs), however, possess ionic nickel arsenide structures with isolated methyl anions. Copper, silver and gold form unstable organo derivatives which show some relation to those of the compounds discussed above. MeCu decomposes above -l5°C and MeAg even at -50°C. p. 78-9oC and (CuPh)" (decomp. 100') are more robust; the structure ofthe former has been determined by X-ray diffraction and consists of four coplanar copper atoms bridged by CH 2 SiMe, groups.
Spectra ofmixtures ofMe 2 Zn and Me 2 Cd with each other or with Me,Al indicate that alkyl exchange occurs readily. The methyl groups in Me 2 Hg, however, exchange only slowly. In solid Ph 2 Hg the two phenyl rings are coplanar. In the di-o-tolyl compound, however, they are twisted through 59° relative to each other, on account of interactions between the ortho substituents on different rings. The dialkyls and diaryls ofberyllium and magnesium are generally associated. Steric effects play an important part in determining the degree of association in beryllium compounds.