Olefins complexes with Lewis acids

Initiation is complicated by dimerization of the Lewis acid and by complexation of the Lewis acid with olefinic double bonds of the monomer. The mechanism of initiation is not clear, although partial monomer... 

Particularly relevant to the present crmtext is the fact that the olefinic double bond is considered as a soft base in Pearson s theory, while many Lewis acids used in cationic polymerisation (BF3, BCI3, AICI3, etc.) are classed as hard acids. Obviously, n-acceptors like chloranil or tetracyanoethylene are considered as soft acids. Thus, the interactions between Lewis acids and olefins must be considered as very weak in the context of the HSAB theory. This prediction is well substantiated by the tenuous character of the complexes observed in experimental studies (see Chap. IV). On the other hand, carbenium ions are usually placed at the borderline between hard and soft acids and are definitely softer than the Lewis acids mentioned above. Consequently, their interactions with olefins must be rather strong, which suggests that that propagation in cationic polymerisations promoted by Lewis acids should be faster than initiation. 

Besides the already mentioned acidic aluminum chloride catalysts, alternative Friedd-Crafts catalysts such as supported acidic tin catalysts have also been developed. The tin-based catalysts were prepared by a method which closely resembled the already mentioned two-step grafting method devised for the aluminum chloride catalyst. Here, SnCU was anchored on silica materials modified with tetraalkylammonium chloride moieties obtained for example, from reaction with [3-(trimethoxysrlyl)propyl]octadecyldimethylammonium chloride, thereafter, reaction of the Lewis acid with the chloride moieties leads to formation of pentacoordinated anionic tin species forming catalytically active complexes (i.e. [R4N][SnCl5] species), associated with the surface. The supported tin catalysts were employed for condensation reactions of olefins with aldehydes forming unsaturated alcohols (Prins condensation. Scheme 5.6-2) [76]. 

The step of cationic initiation can be subdivided into two separate reactions. The first one consists of formation of ionic species and the second one of reactions of these ionic species with the olefins, a cationization process. This reaction, termed priming by Kennedy and Marechal, is a process of ion formation in a non-nucleophilic media through (1) dissociation of protonic acids to form protons and counterions, (2) reactions of Lewis acids with Bronsted acids, (3) dissociation of dimeric Lewis acids, (4) complexation of Lewis acids with water or with alkyl halides or with ethers, and so on. These reactions may take place through a series of complicated steps. The second reaction, the cationization of the olefins, may also include several intermediate steps that will eventually lead to propagating species. 

A sulfinium cation (80) was suggested as a probable intermediate in the ring closure of sulfinyl chlorides by Lewis acids in an intramolecular ene reaction (Kukolja, 1977). The process is visualized as a complexation of the Lewis acid with either the oxygen or the chlorine atom of the sulfinyl chloride followed by formation of the S—C-2 bond with olefinic carbon, concomitant with hydrogen abstraction from the methyl group of the isopropenyl functionality (Scheme 4). In support of this mecha-... 

By the mid-1980s considerable advancements had been made in the field of olefin metathesis chemistry (Grubbs, 2004). This mild carbon-bond-forming reaction was discovered by accident in the late 1960s when researchers at Goodyear exposed a mixture of a-olefins to a combination of tungsten hexachloride and a Lewis acid with the intent to find a new catalyst for the polymerization of vinyl olefins (Calderon et a/., 1968 Calderon et al, 1967). Instead of high polymer the research team observed a complex mixture of scrambled olefin products. The mechanism of this reaction, first proposed by Yves Chauvin (Herrison and Chauvin, 1971) in... 

Finding snch acids (called snperacids ) turned out to be the key to obtaining stable, long-lived alkyl cations and, in general, carbocations. If any deprotonation were still to take place, the formed alkyl cation (a strong Lewis acid) would immediately react with the formed olefin (a good TT-base), leading to the mentioned complex reactions. 

Tetracyanoethylene is colorless but forms intensely colored complexes with olefins or aromatic hydrocarbons, eg, benzene solutions are yellow, xylene solutions are orange, and mesitylene solutions are red. The colors arise from complexes of a Lewis acid—base type, with partial transfer of a TT-electron from the aromatic hydrocarbon to TCNE (8). TCNE is conveniendy prepared in the laboratory from malononitrile [109-77-3] (1) by debromination of dibromoma1 ononitrile [1855-23-0] (2) with copper powder (9). The debromination can also be done by pyrolysis at ca 500°C (10). 

Strong protonic acids can affect the polymerization of olefins (Chapter 3). Lewis acids, such as AICI3 or BF3, can also initiate polymerization. In this case, a trace amount of a proton donor (cocatalyst), such as water or methanol, is normally required. For example, water combined with BF3 forms a complex that provides the protons for the polymerization reaction. 

If the nucleophilicity of the anion is decreased, then an increase of its stability proceeds the excessive olefine can compete with the anion as a donor for the carbenium ion, and therefore the formation of chain molecules can be induced. The increase of stability named above is made possible by specific interactions with the solvent as well as complex formations with a suitable acceptor 112). Especially suitable acceptors are Lewis acids. These acids have a double function during cationic polymerizations in an environment which is not entirely water-free. They react with the remaining water to build a complex acid, which due to its increased acidity can form the important first monomer cation by protonation of the monomer. The Lewis acids stabilize the strong nucleophilic anion OH by forming the complex anion (MtXn(OH))- so that the chain propagation dominates rather than the chain termination. 

Under Lewis-acid-catalyzed conditions, electron-rich arenes can be added to alkenes to generate Friedel-Crafts reaction products. This subject will be discussed in detail in Chapter 7, on aromatic compounds. However, it is interesting to note that direct arylation of styrene with benzene in aqueous CF3CO2H containing H2PtCl6 yielded 30-5% zram-PhCH CHR via the intermediate PhPt(H20)Cl4.157 Hydropheny-lation of olefins can be catalyzed by an Ir(III) complex.158... 

The Lewis acid-Lewis base interaction outlined in Scheme 43 also explains the formation of alkylrhodium complexes 414 from iodorhodium(III) meso-tetraphenyl-porphyrin 409 and various diazo compounds (Scheme 42)398), It seems reasonable to assume that intermediates 418 or 419 (corresponding to 415 and 417 in Scheme 43) are trapped by an added nucleophile in the reaction with ethyl diazoacetate, and that similar intermediates, by proton loss, give rise to vinylrhodium complexes from ethyl 2-diazopropionate or dimethyl diazosuccinate. As the rhodium porphyrin 409 is also an efficient catalyst for cyclopropanation of olefins with ethyl diazoacetate 87,1°°), stj bene formation from aryl diazomethanes 358 and carbene insertion into aliphatic C—H bonds 287, intermediates 418 or 419 are likely to be part of the mechanistic scheme of these reactions, too. 

Osborn s discovery (14) that aluminum halides bimTto oxo ligands in tungsten oxo neopentyl complexes, and that these complexes decompose to give systems which will efficiently metathesize olefins, raised more questions concerning the role of the Lewis acid. A subsequent communication (20) answered some of the questions the aluminum halide removes We oxo ligand and replaces it with two halides to yield neopentylidene complexes (equation 8). 

The following conclusions can be drawn (a) ir-Allylnickel compounds are probably not involved in the catalytic dimerization of cyclooctene, because the highest reaction rate occurs when only traces of these compounds can be detected further, the concentration of the new 7r-allyl-nickel compound (19) becomes significant only after the catalytic reaction has ceased, (b) The complex formed between the original 7r-allylnickel compound (11) and the Lewis acid is transformed immediately upon addition of cyclooctene to the catalytically active nickel complex or complexes. In contrast to 7r-allylnickel compounds, this species decomposes to give metallic nickel on treatment of the catalyst solution with ammonia, (c) The transformation of the catalytically active nickel complex to the more stable 7r-allylnickel complex occurs parallel with the catalytic dimerization reaction. This process is obviously of importance in stabilizing the catalyst system in the absence of reactive olefins. In... 

The route to carbene initiation for systems catalyzed solely by transition metal salts (55, 54), or their combinations with Lewis acids such as A1C13 (55), is not well established. Nevertheless, some evidence suggests reduction of the metal by the olefinic substrate (55). Zero-valent (56) and hexavalent (57, 55) tungsten complexes that promote metathesis when activated by UV radiation are the least-understood metathesis systems. 

Particularly interesting is the reaction of enynes with catalytic amounts of carbene complexes (Figure 3.50). If the chain-length between olefin and alkyne enables the formation of a five-membered or larger ring, then RCM can lead to the formation of vinyl-substituted cycloalkenes [866] or heterocycles. Examples of such reactions are given in Tables 3.18-3.20. It should, though, be taken into account that this reaction can also proceed by non-carbene-mediated pathways. Also Fischer-type carbene complexes and other complexes [867] can catalyze enyne cyclizations [267]. Trost [868] proposed that palladium-catalyzed enyne cyclizations proceed via metallacyclopentenes, which upon reductive elimination yield an intermediate cyclobutene. Also a Lewis acid-catalyzed, intramolecular [2 + 2] cycloaddition of, e.g., acceptor-substituted alkynes to an alkene to yield a cyclobutene can be considered as a possible mechanism of enyne cyclization. 

---