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Extra info for Principles of Organometallic Chemistry
Sample text
Similar weak association may also occur in solid triphenylindium. r. studies show that exchange of methyl groups between Me,M molecules (M = Ga, In. TI) occurs readily, presumably through methyl bridged dimers. The Group IIB dialkyls and diaryls are ali monomeric, having linear skeletons in which the metal is 2-coordinate. 929 Â: Cd-C. 005 Â. The anomalous position of cadmium is reflected also in the boiling point sequence (p. 6) and is attributed to bigger van der Waals forces between Me 2 Cd than between Me 2 Hg molecules.
Fig. 3). The highly polar character of organolithium compounds causes strong association. The geometry ofthe coordination sphere is determined essentially by steric effects, as in ionic structures, rather than by interaction of electron pairs. Even where lithium may appear to possess an octet configuration, it is not envisaged that the electrons are strongly held by the valence orbitals ofthe metal in covalent bonds. Crystalline methyllithium consists of tetrameric aggregates (Fig. 4). Each carbon atom is bound to three hydrogen atoms and is equidistant from the three lithium atoms which are at the corners of a triangular face of the Li 4 tetrahedron.
B) The Li 4 C4 skeleton of the tetramer viewed approximately along one of threefold axes. 2C 6 H6 • Cyclohexyl groups occupy six of the eight triangular faces of the octahedron- only two shown. 2. Aggregation of organolithiums, (RLi)n in solution RLi MeLi EtLi Bu"Li su•u Bu1Li PhLi Menthyl Li Solvent Paraffins or cyclohexane Benzene or toluene Diethyl ether Tetrahydrofuran Insol Insol 4 4 4 4 4 4 4 4 2 2 6 4-6 4 4 2 6 6 4 4 -Not known to author. In (MeLi) 4 TMEDA (TMEDA = Me 2 NCH 2 CH 2 NMe 2 or tetramethylethylenediamine, 1.