Mechanisms, ionic

Binuclear oxidative additions, because they involve e rather than 2e changes at the metals, often go via radicals. One of the best known examples is shown in Eq. 6.21. 

The rate-determining step is net abstraction of a halogen atom ftom RX by tbe odd-electron Co(FI) (Eq, 6.22) the resulting R combines with a second Co(II) 

In reactions involving radicals, it is important to use solvents that do not react fast with R alkane, CeH6, AcOH, CHjCN, and water are usually satisfactory. 

The rate of the second type (Eq. 6.25) usually follows the rate equation shown in Eq. 6.27, suggesting that Cl addition is the slow step. This step can be carried out independently with LiCl alone, but no reaction is observed with HBF4 alone because the cationic iridium complex is not basic enough to protonate and BF4 is a noncoordinating anion. 

Other acids (or Lewis acids), which are ionized to some extent in solution, such as RCO2H and HgClj (Eqs. 6.28 and 6.29), may well react by the same mechanism, but this has not yet been studied in detail. 

Hydrogen halides are often largely dissociated in solution, and the anion and proton tend to add to metal complexes in separate steps. Two variants have been recognized. In the more common one, the complex is basic enough to 

The convenience of this technique has led to the development of many commercial products, including thermoplastic elastomers based on triblocks of styrene, butadiene, and isoprene. The initiator used in these systems is based on hydrocarbon-soluble organolithium initiators. In some cases, a hydrocarbon-soluble dilithio initiator has been employed in the preparation of multiblock copolymers. Several techniques are used to prepare thermoplastic elastomers of the ABA type. All these are discussed in detail in Chapter 2. A short summary of these techniques is given here. 

In this two-stage process, B is sequentially polymerized onto A, and then the two chains are coupled to yield an ABBA block copolymer. Triblocks of SBS have been prepared using this method, with methylene dichloride as the coupling agent. The disadvantage is the formation of radical anions, which can lead to contamination of the triblock with multiblock species. 

This method is used to form a block copolymer, which consists of two segments of essentially homopolymeric stracture separated by a block of a tapered segment of random copolymer composition. These are usually prepared by taking advantage of the differences in reaction rates of the component monomers. When polymerized individually in hexane, butadiene reacts six times more slowly than styrene however, when styrene and butadiene are copolymerized in a hydrocarbon solvent such as hexane, the reaction rates reverse, and the butadiene becomes six times faster than the styrene. This leads to a tapering of the styrene in a copolymerization reaction. For more details on the synthesis techniques, refer to Chapters 2 and 13. 

In a polar solvent, where HX (X = Cl, Br, I) can dissociate, X and H+ often give a two-step OA with L M. The metal usually protonates first, followed by X binding to give L M(H)(X) (Eq. 6.19) rarer is X attack, followed by protonation (Eq. 6.20). The first path is favored by basic 

---

Such reactions can be initiated by free radicals, derived from compounds (initiators) such as benzoyl peroxide, ammonium persulphate or azobis-isobutyronitrile or by ionic mechanisms... 

It might be noted that most (not all) alkenes are polymerizable by the chain mechanism involving free-radical intermediates, whereas the carbonyl group is generally not polymerized by the free-radical mechanism. Carbonyl groups and some carbon-carbon double bonds are polymerized by ionic mechanisms. Monomers display far more specificity where the ionic mechanism is involved than with the free-radical mechanism. For example, acrylamide will polymerize through an anionic intermediate but not a cationic one, A -vinyl pyrrolidones by cationic but not anionic intermediates, and halogenated olefins by neither ionic species. In all of these cases free-radical polymerization is possible. 

Ionic polymerizations, whether anionic or cationic, should not be judged to be unimportant merely because our treatment of them is limited to two sections in this text. Although there are certain parallels between polymerizations which occur via free-radical and ionic intermediates, there are also numerous differences. An important difference lies in the more specific chemistry of the ionic mechanism. While the free-radical mechanism is readily discussed in general terms, this is much more difficult in the ionic case. This is one of the reasons why only relatively short sections have been allotted to anionic and cationic polymerizations. The body of available information regarding these topics is extensive enough to warrant a far more elaborate treatment, but space limitations and the more specific character of the material are the reasons for the curtailed treatment. 

Both modes of ionic polymerization are described by the same vocabulary as the corresponding steps in the free-radical mechanism for chain-growth polymerization. However, initiation, propagation, transfer, and termination are quite different than in the free-radical case and, in fact, different in many ways between anionic and cationic mechanisms. Our comments on the ionic mechanisms will touch many of the same points as the free-radical discussion, although in a far more abbreviated form. 

However, reaction 7 suffers other shortcomings, eg, entropy problems. Other proposals range from trace peroxidic contaminants to ionic mechanisms for generating peroxides (1) to cosmic rays (17). In any event, the initiating reactions are significant only during the induction period (18). 

Hydrogen haHde addition to vinyl chloride in general yields the 1,1-adduct (50—52). The reactions of HCl and hydrogen iodide [10034-85-2], HI, with vinyl chloride proceed by an ionic mechanism, while the addition of hydrogen bromide [10035-10-6], HBr, involves a chain reaction in which a bromine atom [10097-32-2] is the chain carrier (52). In the absence of a transition-metal catalyst or antioxidants, HBr forms the 1,2-adduct with vinyl chloride (52). HF reacts with vinyl chloride in the presence of stannic chloride [7646-78-8], SnCl, to form 1,1-difluoroethane [75-37-6] (53). 

A considerable amount of hydrobromic acid is consumed in the manufacture of inorganic bromides, as well as in the synthesis of alkyl bromides from alcohols. The acid can also be used to hydrobrominate olefins (qv). The addition can take place by an ionic mechanism, usually in a polar solvent, according to Markownikoff s rule to yield a secondary alkyl bromide. Under the influence of a free-radical catalyst, in aprotic, nonpolar solvents, dry hydrogen bromide reacts with an a-olefin to produce a primary alkyl bromide as the predominant product. Primary alkyl bromides are useful in synthesizing other compounds and are 40—60 times as reactive as the corresponding chlorides (6). 

Halobutyls. Chloro- and bromobutyls are commercially the most important butyl mbber derivatives. The halogenation reaction is carried out in hydrocarbon solution using elemental chlorine or bromine (equimolar ratio with enchained isoprene). The halogenation is fast, and proceeds mainly by an ionic mechanism. The stmctures that may form include the following ... 

The reactions are highly exothermic. Under Uquid-phase conditions at about 200°C, the overall heat of reaction is —83.7 to —104.6 kJ/mol (—20 to —25 kcal/mol) ethylene oxide reacting (324). The opening of the oxide ring is considered to occur by an ionic mechanism with a nucleophilic attack on one of the epoxide carbon atoms (325). Both acidic and basic catalysts accelerate the reactions, as does elevated temperature. The reaction kinetics and product distribution have been studied by a number of workers (326,327). 

Pyrroles, furans and thiophenes undergo photoinduced alkylation with diarylalkenes provided that the alkene and the heteroaromatic compound have similar oxidation potentials, indicating that alkylation can occur by a non-ionic mechanism (Scheme 20) (81JA5570). 

A number of important addition polymers are produced by ionic mechanisms. Although the process involves initiation, propagation and termination stages the growing unit is an ion rather them a radical. 

The initial discussion in this chapter will focus on addition reactions. The discussion is restricted to reactions that involve polar or ionic mechanisms. There are other important classes of addition reactions which are discussed elsewhere these include concerted addition reactions proceeding through nonpolar transition states (Chapter 11), radical additions (Chapter 12), photochemical additions (Chapter 13), and nucleophilic addition to electrophilic alkenes (Part B, Chi iter 1, Section 1.10). 

The anti-Markownikoff addition of hydrogen bromide to alkenes was one of the earliest free-radical reactions to be put on a firm mechanistic basis. In the presence of a suitable initiator, such as a peroxide, a radical-chain mechanism becomes competitive with the ionic mechanism for addition of hydrogen bromide ... 

This ionic mechanism is supported by kinetic data. A free radical mechanism has been proposed for the unique bromination (with bromine) of 3a, 12a-diacetoxypregnan-20-one ethylene ketal, which gives the 21-bromo derivative in excellent yield. ... 

Replacement of hydrogen with halogen in fluoraarenes takes place by an ionic mechanism and is subject to the normal directing effects [27, 28, 29] (equations 13-15). 

With a suitable combination of electron-deficient fluoroalkene and electron-rich addend, cycloaddition can proceed by a dipolar mechanism involving zwitte-rion intermediates Like Us isomer, l,2-bis(trifluoromethyl)-l,2-dicyanoethylene [85], l,l-bis(trifluoromethyl)-2,2-dicyanoethylene forms cyclobutanes by an ionic mechanism [104, 105, 106] (equations 39 and 40)... 

Ynamines also react with many fluorinated alkenes by an ionic mechanism to give fluorocyclobutenes, accompanied by varying amounts of diene depending on the fluoroalkene [107, 108] (equation 41). 

Studies of solvolysis of similar polyfluonnated polycyclic aromatic systems, such as 2,3-(tetrafluorobenzo)bicyclo[2 2 2]octadienes and related compounds, proved the ionic mechanism of this rearrangement [55, 36, 37] (equation 9) Possible nonclassical carbonium ion involvement has been discussed [5S, 39, 40, 41]... 

The reactions of electrophilic alkenes (alkenes attached to electron-withdrawing groups) with enamines produce one or more of the following products simple alkylation (2), 1,2 cycloaddition (3), and 1,4 cycloaddition (4). Competition with C alkylation by N alkylation is inconsequential and therefore will be largely ignored (5,7). A stepwise ionic mechanism leading to these products necessarily involves the formation of a zwitterion intermediate (1) as the first step, which is then followed either by one of the... 

Thermal decomposition of lead tetraacetate gives rise to methyl radicals, again through the initial formation of acetoxy radicals. " An ionic mechanism for the decomposition has also been postulated, and it is possible that both mechanisms may occur, depending on the conditions. 

Although alternative ionic mechanisms have been formulated," the essential feature of the reaction, namely the generation of free hydroxyl radicals, is now generally accepted." ... 

Furthermore in certain cases Diels-Alder reactions may proceed by an ionic mechanism. 

The electrical conductivity of PET fibers as compared with other main synthetic fibers is relatively low. This explains why PET fibers are often utilized in the manufacture of textiles as electroisolating materials. The value of the electrical resistivity characterizing reciprocal conductivity is of the order 10 (/2 cm). The mechanism of the electrical conductivity of PET fibers is still a matter of controversy. According to results attained [57], there are convincing arguments that in the case of PET objects the electrical conductivity is due to the ionic mechanism. 

There is also evidence that the adsorbed gases may be charged this led Vlasenko and Uzefovich to develop a completely ionic mechanism (4) in which the bracket, [ ], represents a metallic site ... 

Monomers that are strong electron donors may undergo spontaneous oupolymeri/.aliun with strong electron acceptor monomers by a radical mechanism. In certain cases homopolymers formed by an ionic mechanism accompany copolymer formation.312,j2s... 

---