Alkyls, metal

Polyacetaldehyde, a mbbery polymer with an acetal stmcture, was first discovered in 1936 (49,50). More recentiy, it has been shown that a white, nontacky, and highly elastic polymer can be formed by cationic polymerization using BF in Hquid ethylene (51). At temperatures below —75° C using anionic initiators, such as metal alkyls in a hydrocarbon solvent, a crystalline, isotactic polymer is obtained (52). This polymer also has an acetal [poly(oxymethylene)] stmcture. Molecular weights in the range of 800,000—3,000,000 have been reported. Polyacetaldehyde is unstable and depolymerizes in a few days to acetaldehyde. The methods used for stabilizing polyformaldehyde have not been successful with poly acetaldehyde and the polymer has no practical significance (see Acetalresins). 

Metal Alibis and Alkoxides. Metal alkyls (eg, aluminum boron, sine alkyls) are fairly active catalysts. Hyperconjugation with the electron-deficient metal atom, however, tends to decrease the electron deficiency. The effect is even stronger in alkoxides which are, therefore, fairly weak Lewis acids. The present discussion does not encompass catalyst systems of the Ziegler-Natta type (such as AIR. -H TiCl, although certain similarities with Friedel-Crafts systems are apparent. 

The other commercially important routes to alkyltin chloride intermediates utilize an indirect method having a tetraalkjitin intermediate. Tetraalkyltins are made by transmetaHation of stannic chloride with a metal alkyl where the metal is typicaHy magnesium or aluminum. Subsequent redistribution reactions with additional stannic chloride yield the desired mixture of monoalkyl tin trichloride and dialkyltin dichloride. Both / -butjitin and / -octjitin intermediates are manufactured by one of these schemes. 

Ketenes can react in several ways with organometaUic compounds and complexes. They can add as ligands to coordinated metals forming stable ketene, ketenyl, and ketenyfldene complexes. Ketenes can be inserted into metal—hydride, metal—alkyl, metal—OR, and metal—NR2 bonds, react with metal—oxide complexes, and with coordinated Hgands. This chemistry has been reviewed (9,51). 

Polymerization occurs at active sites formed by interaction of the metal alkyl with metal chloride on the surface of the metal chloride crystals. Monomer is chemisorbed at the site, thus accounting for its orientation when added to the chain, and propagation occurs by insertion of the chemisorbed monomer into the metal—chain bond at the active site. The chain thus grows out from the surface (31). Hydrogen is used as a chain-transfer agent. Chain transfer with the metal alkyl also occurs. 

Alkoxides of nonmetals are described in articles about the corresponding compounds (see Boron COMPOUNDS, Boron oxides Silicon compounds). Metal alkyls, in which the alkyl group is bound direcdy to the metal, are also discussed elsewhere (see Aluminum compounds). 

Historically, among the most important reactions of siUcon haUdes are those occurring with metal alkyls and metal alkyl haUdes. The Grignard reaction, for example, was the first commercial process for manufacturing organosiUcon compounds, which were later converted to siUcones (19). 

Metals and metalloids that form alkyl compounds, eg, methylmercury and methylarsenic acid, tributjltin, deserve special concern because these compounds are volatile and accumulate in cells they are poisonous to the central nervous system of higher organisms. Because methylmercury or other metal alkyls may be produced at a rate faster than it is degraded by other organisms, it may accumulate in higher organisms such as fish. Hg species are also reduced to elementary Hg which is soluble in water but lost by volatilization to the atmosphere (40). 

Using a solution process, the choice of catalyst system is determined, among other things, by the nature of the third monomer and factors such as the width of the mol wt distribution to be realised in the product. A number of articles review the induence of catalyst systems on the stmctural features of the products obtained (3,5—7). The catalyst comprises two main components first, a transition-metal haHde, such as TiCl, VCl, VOCl, etc, of which VOCl is the most widely used second, a metal alkyl component such as (C2H )2A1C1 diethylalurninum chloride, or monoethyl aluminum dichloride, (C2H )AlCl2, or most commonly a mixture of the two, ie, ethyl aluminum sesquichloride, [(C2H )2Al2Cl2]. 

One of the earliest studies of deposition from organometallics was the discovery that when some metal alkyls, such as lead tetramethyl Pb(CH3)4,... 

The process of anionic polymerisation was first used some 60 or more years ago in the sodium-catalysed production of polybutadiene (Buna Rubbers). Typical catalysts include alkali metals, alkali metal alkyls and sodium naphthalene, and these may be used for opening either a double bond or a ring structure to bring about polymerisation. Although the process is not of major importance with the production of plastics materials, it is very important in the production of synthetic rubbers. In addition the method has certain special features that make it of particular interest. 

Some materials sueh as oil-impregnated eotton and iron pyrites are prone to spontaneous eombustion, whilst seleeted materials sueh as metal alkyls and metals in a finely divided state burn on immediate eontaet with water or air. These are termed pyrophorie . Examples and preeautions for their eontrol are deseribed in Chapter 6. 

The next major commodity plastic worth discussing is polypropylene. Polypropylene is a thermoplastic, crystalline resin. Its production technology is based on Ziegler s discovery in 1953 of metal alkyl-transition metal halide olefin polymerization catalysts. These are heterogeneous coordination systems that produce resin by stereo specific polymerization of propylene. Stereoregular polymers characteristically have monomeric units arranged in orderly periodic steric configuration. 

Reactivity and yields are greatly enhanced by the presence of 0.5-1% Na in the Li. The reaction is also generally available for the preparation of metal alkyls of the heavier Group 1 metals. Lithium aryls are best prepared by metal-halogen exchange using LiBu" and an aryl iodide, and transmetalation is the most convenient route to vinyl, allyl and other unsaturated derivatives ... 

The reverse reaction (formation of metal alkyls by addition of alkenes to M-H) is the basis of several important catalytic reactions such as alkene hydrogenation, hydroformylation, hydroboration, and isomerization. A good example of decomposition by y3-elimination is the first-order intramolecular reaction ... 

Stable transition-metal complexes may act as homogenous catalysts in alkene polymerization. The mechanism of so-called Ziegler-Natta catalysis involves a cationic metallocene (typically zirconocene) alkyl complex. An alkene coordinates to the complex and then inserts into the metal alkyl bond. This leads to a new metallocei e in which the polymer is extended by two carbons, i.e. 

Variations and Improvements on Alkylations of Chiral OxazoUnes Metalated chiral oxazolines can be trapped with a variety of different electrophiles including alkyl halides, aldehydes,and epoxides to afford useful products. For example, treatment of oxazoline 20 with -BuLi followed by addition of ethylene oxide and chlorotrimethylsilane yields silyl ether 21. A second metalation/alkylation followed by acidic hydrolysis provides chiral lactone 22 in 54% yield and 86% ee. A similar... 

Tp )FeMe] [Tp = phenyltris(3-tert-butylpyrazol-l-yl)borate] (98JA10561) and [(> -Tp )FeR] [Tp = hydrotris(3,5-diisopropylpyrazol-l-yl)borate R = Ft, CH2CHCH2, CH2T0I-P] [98JCS(CC)973, 99JCS(CC)417] are prepared by methods similar to those described for the similar non-transition and late-transition metal alkyls. 

At the second stage the decomposition of metal alkyl takes place. Metal alkyl is liable to decompose into metal alkyl and olefin causing the increased saturation of polyethylene macromolecules ... 

Metal alkyl is liable to decompose with breaking of the carbon-carbon bond that is in )3-position relative to the C—Me bond ... 

The resultant metal alkyl is rapidly decomposed at temperatures from 200-250°C with the formation of metal, alkanes, and alkenes C2—C3. 

Metal alkyl reacts with nonsaturated ends of macromolecules following the pattern of substitution reaction [and causing a decrease in the number of methyl groups] ... 

Metalated Ally lie Sulfones I.5.2.2.2.I. Metalated Alkyl Sulfones Simple Diastereoselection... 

Another group of Japanese workers91 found that the sulphoxonium salt, 7, was reducible to sulphoxides with either alkyllithiums or lithium dialkylcuprates, the exact reaction pathway being complicated by halide ions originating from the preparation of the metal alkyls. However, good yields of methyl phenyl sulphoxide were obtained by reduction of 7 with sulphur dioxide or a thiol in pyridine (equation 37). 

Eisch, Behrooz and Galle196 give compelling evidence for the intervention of radical species in the desulphonylation of certain acetylenic or aryl sulphones with metal alkyls having a lower oxidation potential at the anionic carbon. The primary evidence presented by these workers is that the reaction of 5-hexenylmagnesium chloride outlined in equation (85) gives a mixture of desulphonylation products, in accord with the known behaviour of the 5-hexenyl radical, in which the cyclopentylmethyl radical is also formed. 

Schrock-type carbenes are nucleophilic alkylidene complexes formed by coordination of strong donor ligands such as alkyl or cyclopentadienyl with no 7T-acceptor ligand to metals in high oxidation states. The nucleophilic carbene complexes show Wittig s ylide-type reactivity and it has been discussed whether the structures may be considered as ylides. A tantalum Schrock-type carbene complex was synthesized by deprotonation of a metal alkyl group [38] (Scheme 7). 

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