Organolithium compounds, structure

The crystal structures of many organolithium compounds have been determined.44 Phenyllithium has been crystallized as an ether solvate. The structure is tetrameric with lithium and carbon atoms at alternating corners of a highly distorted cube. The lithium atoms form a tetrahedron and the carbons are associated with the faces of the tetrahedron. Each carbon is 2.33 A from the three neighboring lithium atoms and an ether molecule is coordinated to each lithium atom. Figures 7.2a and b show, respectively, the Li-C cluster and the complete array of atoms, except for hydrogen 45 Section 6.2 of Part A provides additional information on the structure of organolithium compounds. 

Summary Fluorosilylamines and -hydrazines react with organolithium compounds to yield stable lithium derivatives. Perfluoro (Si-N) four- and six-membered ring systems are obtained with SiF4. The synthesis and crystal structures of the compounds are discussed. 

Transmetallation with RLi is used to prepare pure organolithium compounds for structural and spectroscopic studies. 

SN2 reactions of primary organolithium compounds on PMMA in dilute homogeneous solution may be considered as a model system where all the important reaction parameters may be controlled they allow both a quantitative analysis of PMMA chain reactivity and the synthesis of well defined ketonic copolymers within a wide range of possible structural variations. The two homologous series of organolithium compounds and the corresponding reaction conditions we selected are given below ... 

The use of sterically hindered secondary organolithium reagents, such as (CgH jCH Li, drastically favors the O-alkyl scission of thejbster group (37) finally, organolithium compounds leading to non enolizable keto functions in the first step of substitution, such as C H Li, promote competitive and consecutive reactions resulting in complex copolymers of poorly defined structure (38,39) ... 

Improvements of the theoretical methodologies during the past few years have resulted in valuable corrections in the proposed structures. The availability of accurate structural and energetic data has encouraged detailed mechanistic studies of the reactions of organolithium compounds. These are discussed in the next section. 

Many reactions exhibited by organolithium compounds are studied theoretically. The structure, energy and bonding discussed above have direct consequences in determining the reaction paths. The large variety of the reactions of organolithium compounds studied theoretically are discussed below. 

It has been found that the Li quadrupole parameters x( Li) and /]( Li) are sensitive probes of solid state structures of organolithium compounds, for example with respect to aggregate size, solvation, ion pair structure and the X-Li-X structural angle. These results will be discussed in the following sections. 

SCHEME 5. Structures of organolithium compounds with different C—Li—C angles... 

As mentioned in Sections I.B.2.b and II.A, the dipolar coupling between Li- C may complicate solid state NMR spectra of organolithium compounds and its elimination is often desirable. On the other hand, dipolar coupling constants are related to atomic distances and their determination can yield important structural information. It is therefore of general interest that the REDOR technique, briefly described in Section I.B.2.b, provides a means to determine these parameters. 

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