Lithium alkyls structure

Polymers containing 90-98% of a c 5-1,4-structure can be produced using Ziegler-Natta catalyst systems based on titanium, cobalt or nickel compounds in conjuction with reducing agents such as aluminium alkyls or alkyl halides. Useful rubbers may also be obtained by using lithium alkyl catalysts but in which the cis content is as low as 44%. 

Heterocyclic structures analogous to the intermediate complex result from azinium derivatives and amines, hydroxide or alkoxides, or Grignard reagents from quinazoline and orgahometallics, cyanide, bisulfite, etc. from various heterocycles with amide ion, metal hydrides,or lithium alkyls from A-acylazinium compounds and cyanide ion (Reissert compounds) many other examples are known. Factors favorable to nucleophilic addition rather than substitution reactions have been discussed by Albert, who has studied examples of easy covalent hydration of heterocycles. 

On the basis of reaction-product structures, it might be expected that the reactions of organic halides with sodium naphthalene (Scheme 9) might resemble mechanistically the reactions of organic halides with lithium alkyls. CIDNP studies have shown that they are in fact quite different, in particular in the mechanism by which polarization occurs. The observations are as follows (Garst et al., 1970). 

A great deal of effort has been directed to determining the structures of lithium alkyls. It has been determined that in hydrocarbon solutions the dominant species is a hexamer when the alkyl groups are small. In the solid phase, the structure is body-centered cubic with the (LiCH3)4 units at each lattice site. Each unit is a tetramer in which the four lithium atoms reside at the comers of a tetrahedron and the methyl groups are located above the centers of the triangular faces. The carbon atoms of... 

In pure EtjO (without added THF) the reaction times are considerably lengthened. Accordingly, in the first reaction step, a P—P bond of 85 is cleaved by the nucleophilic attacking lithium alkyL Because of the symmetrical structure of 85 only one primary product can be yielded by the opening of its four-membered ring. When cooled THF is added to this solution of compound 86, or of 87, rapid isomerization to the P2 n-tetraphosphide follows, as illustrated by Eq. (14). 

The field of R3C lithium organic structures is wide and we wiU concentrate on those with alkyl-, aryl- and silyl-substituted anions. Heteroatom-snbstitnted lithinm organics will just be mentioned briefly. 

Let us now focus our attention on the interaction between lithium alkyls and Group III derivatives. These species are often considered to be metalates with discrete MR4 ions present, but a variety of studies show that substantial metal-anion interactions occur both in solution and in the solid state (45, 96, 131). More thorough examination of both of the structures and spectroscopic properties of these derivatives shows that they must be included in any treatment involving electron-deficient bonding. 

The ladder structures formed by lithium amides and their heavier group 15 analogues stand in contrast to those formed by the related lithium alkyls which generally prefer aggregates with three-dimensional or one-dimensional polymeric structures. 

In solution lithium alkyls are extensively associated especially in non-polar solvents. Ethyllithium in benzene solution exists largely as a hexamer (9, 43) in the concentration range down to 0.1 molar and there is no evidence for a trend with concentration so presumably the hexamers persist to even lower concentrations. Indeed even in the gas phase at high dilution it exists as hexamer and tetramer in almost equal amounts (3). In a similar way n-butyllithium in benzene or cyclohexane is predominantly hexameric (62, 122). t-Butyl-lithium however is mostly tetrameric in benzene or hexane (115). In ether solution both lithium phenyl and lithium benzyl exist as dimers (122) and it has been suggested that butyllithium behaves similarly in ether (15) although this does not agree with earlier cryoscopic measurements (122). It is however certain that more strongly basic ethers cause extensive breakdown of the structure. 

The polymer formed from isoprene with lithium has a predominantly cis-1,4 structure whereas that from the other alkali metals has a more mixed microstructure (103). The predominantly cis-1,4 configuration is retained on dilution with hydrocarbon solvents and with lithium alkyls, but in polar solvents 3,4 linkages predominate (44, 45). With butadiene... 

Some information is available on other acrylates. N,N-disubstituted acrylamides form isotactic polymers with lithium alkyls in hydrocarbons (12). t-Butylacrylate forms crystallizable polymers with lithium-based catalysts in non-polar solvents (65) whereas the methyl, n-butyl, sec-butyl and isobutyl esters do not. Isopropylacrylate also gives isotactic polymer with lithium compounds in non-polar solvents (34). The inability of n-alkylacrylates to form crystallizable polymers may result from a requirement for a branched alkyl group for stereospecific polymerization. On the other hand lack of crystallizability cannot be taken as definite evidence of a lack of stereoregulating influence, as sometimes quite highly regular polymer fails to crystallize. The butyllithium-initiated polymers of methylmethacrylate for instance cannot be crystallized. The presence of a small amount of more random structure appears to inhibit the crystallization process1. 

Solution (S-SBR) consists of styrene butadiene copolymers prepared in solution. A wide range of styrene-butadiene ratios and molecular structures is possible. Copolymers with no chemically detectable blocks of polystyrene constitute a distinct class of solution SBRs and are most like slyrcnc-buladicne copolymers made by emulsion processes. Solution SBRs with terminal blocks of polystyrene (S-B-S) have the properties of self-cured elastomers. They are processed like thermoplastics and do not require vulcanization. Lithium alkyls are used as the catalyst. 

Fig. 1. Structures of alkyllithium tetramers and hexamers (a) tetrahedron of lithium alkyl groups (b) arrangement of alkyl groups around octahedron of...

Lithium alkyls or aryls add to pseudoazulenes 3398100 and 39.113-114 The carbanion always reacts with the carbon atom opposite the heteroatom in the six-membered ring (Scheme 16). After hydrolysis of primary intermediate 121 dihydro products (122) are formed, which can be transformed to pseudoazulenes in the usual manner (see Section III,A,2). The structure of primary intermediate 121 is confirmed by its alkylated (or acylated) products (123). Even these compounds can easily be dehydrogenated to pseudo-azulene. In this way. substituted pseudoazulenes can be formed that are not obtainable otherwise. The direction of addition to the pseudoazulenes is the same as in azulenes.241... 

These compounds are formed by addition of lithium alkyls to alkylpyrazines, followed by hydrolysis (see Section V,A). They readily oxidize to pyrazines on exposure to air. Some early examples of 1,4-dihydropyrazines have recently been shown to have 1,2-dihydro structures.384 ... 

However, the well-known ability of organolithium compounds to form associated species or to form complexes with electron donor compounds (240—242) provides strong support for mechanisms involving cationic attack by the lithium cation on the monomer prior to an anionic addition. With three orbitals available for coordination, a monomeric lithium alkyl should be able to complex both double bonds of a diolefin to provide the orientation for making cis-1,4 polymer and still have an orbital available for forming associated species in hydrocarbon solvents. The lithium orbitals are presumed to be directed tetrahedrally. Looking at the top of a tetrahedron with the fourth lithium oibital above and normal to the plane of the paper, the complex could have structure A below. In the transition state B for the addition step, the structure... 

The structures of the organic derivatives of the Group IA and IIA metals are not simple because many of them involve molecular association. For example, the lithium alkyls are tetramers in which the lithium atoms reside at the corners of a tetrahedron and the carbon atoms bonded to them are located above the triangular faces of the tetrahedron as shown in Figure 7.2. 

The character of the counterion and the solvent both affect the microstruclure of polymers made anionically from dienes. In general, the proportion of 1,4 chains is highest for Li and decreases with decreasing clecironegativity and increasing size of the alkali metals in the order Li > Na > K > Rb > Cs. A very high (>90%) 1,4 content is achieved only with lithium alkyl or lithium metal initiation in hydrocarbon solvents. The properties of polymers of conjugated diolefins tend to be like those of thermoplastics if the monomer enchainment is 1,2 or 3,4 [reactions (4-3) and (4-4)]. Elastomeric behavior is realized from 1,4 polymerization and particularly if the polymer structure is cis about ihe residual double bond. 

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