Metal alkenes preparation

Probably the first metal alkene complex was Zeise s salt, K[Pt(C2H4)Cl3] or the bridged compound [PtCl2(C2H4)]2. These compounds were first prepared by Zeise in about 1825. The palladium analogs of these compounds are also now known. A large number of metal alkene complexes are known, and some of the chemistry of these materials will be described here. 

A number of synthetic methods are useful for preparing metal alkene complexes. A few of the more general ones will be described here, but the suggested readings given at the end of the chapter should be consulted for more details. 

Finally perfluorinated alkenes, prepared according to various routes (decarboxylation of perfluorinated acids or anhydrides, action of organolithium, magnesium reagents or metallic zinc-copper couple to perfluoroalkyl iodides, oligomerisation of TFE and of HFP, addition of perfluoroalkyl iodides to per-fluoroallyl chloride [304], addition of KF to perhalogenated esters or alkanes... 

For the preparation of conjugated alkynes, one can alkenylate or arylate alkynes according to Section 13.3.4. Alternatively, metallated alkenes or metallated aromatic compounds also may be alkynylated, but this option will not be pursued further. We merely mention in passing that bromoalkynes and iodoalkynes are suitable alkynylat-ing agents and that these can be obtained in a one-step reaction from terminal alkynes ... 

This result was confirmed and extended by Oliver and coworkers in a series of reports dealing with the intramolecular attack of a variety of organometallics7 (Al, Mg, Li, Zn, etc.) onto unactivated alkenes. When 4 was prepared from di(5-hexenyl)mercury, it cyclized to 5 in less than 1 h at 25 °C in diethyl ether and these cyclization reactions were thought to be promoted by metal-alkene complexation8, that required metals bearing empty orbitals. Moreover, the rate of cyclization is highly solvent-dependent at 25 °C 4 takes 8 days to cyclize in pentane, 96 h in benzene and less than an hour in diethyl ether. 

Other complexes of great interest are the / -conjugated diene metallocenes. They are conveniently prepared by the one-pot reaction of the photochemically induced metallocene with the diene at low temperature. Alternative routes include the treatment of the metallocene dichloride with a conjugated diene dianion equivalent or the coupling of alkenyl ligands in the coordination sphere of the metal. The resulting systems show unusual behavior. For example, buta-1,3-diene directly leads to the s-trans complex (8), which can be thermally equilibrated into the s-cis isomer (9). This form exhibits a substantial metallacyclopentene character and is best described as a d metal (cr, 7r)-type complex (10), as shown by X-ray crystal analysis. On the other hand, the s-trans isomer should be formally regarded as a real d metal -alkene 7T-complex. 

Highly reactive metallic titanium, prepared from TiCb and potassium, reduces enol phosphates to alkenes, permitting regioselective synthesis of dienes from a,p-unsaturated ketones. ... 

Similar cross-coupling procedures have been used to prepare styrenes by the reaction of metalated aromatics with vinyl halides/triflates or, conversely, metalated alkenes with aromatic halides/triflates in the presence ofPd(Ph3P)4 (eq 6). Typically, ArCl are poor substrates in Pd(PPh3)4-catalyzed coupling reactions. However, by forming the chromium tricarbonyl complex of the aryl chloride, a facile coupling reaction with vinyl-stannanes can be achieved (eq 7). ... 

The alka-l,2,4-trienes (ailenylaikenes) 12 are prepared by the reaction of methyl propargyl carbonates with alkenes. Alkene insertion takes place into the Pd—C bond of the ailenyipailadium methoxide 4 as an intermediate and subsequent elimination of/3-hydrogen affords the 1,2,4-triene 12. The reaction proceeds rapidly under mild conditions in the presence of KBr. No reaction takes place in the absence of an alkali metal salt[4j. 

There are a wide variety of methods for introduction of substituents at C3. Since this is the preferred site for electrophilic substitution, direct alkylation and acylation procedures are often effective. Even mild electrophiles such as alkenes with EW substituents can react at the 3-position of the indole ring. Techniques for preparation of 3-lithioindoles, usually by halogen-metal exchange, have been developed and this provides access not only to the lithium reagents but also to other organometallic reagents derived from them. The 3-position is also reactive toward electrophilic mercuration. 

A useful alternative to catalytic partial hydrogenation for converting alkynes to alkenes IS reduction by a Group I metal (lithium sodium or potassium) m liquid ammonia The unique feature of metal-ammonia reduction is that it converts alkynes to trans alkenes whereas catalytic hydrogenation yields cis alkenes Thus from the same alkyne one can prepare either a cis or a trans alkene by choosing the appropriate reaction conditions... 

The preparation and structure determination of ferrocene marked the beginning of metallocene chemistry Metallocenes are organometallic compounds that bear cyclo pentadiemde ligands A large number are known even some m which uranium is the metal Metallocenes are not only stucturally interesting but many of them have useful applications as catalysts for industrial processes Zirconium based metallocenes for example are the most widely used catalysts for Ziegler-Natta polymerization of alkenes We 11 have more to say about them m Section 14 15... 

A number of less hindered monoalkylboranes is available by indirect methods, eg, by treatment of a thexylborane—amine complex with an olefin (69), the reduction of monohalogenoboranes or esters of boronic acids with metal hydrides (70—72), the redistribution of dialkylboranes with borane (64) or the displacement of an alkene from a dialkylborane by the addition of a tertiary amine (73). To avoid redistribution, monoalkylboranes are best used /V situ or freshly prepared. However, they can be stored as monoalkylborohydrides or complexes with tertiary amines. The free monoalkylboranes can be hberated from these derivatives when required (69,74—76). Methylborane, a remarkably unhindered monoalkylborane, exhibits extraordinary hydroboration characteristics. It hydroborates hindered and even unhindered olefins to give sequentially alkylmethyl- and dialkylmethylboranes (77—80). 

Primary dialkylboranes react readily with most alkenes at ambient temperatures and dihydroborate terminal acetylenes. However, these unhindered dialkylboranes exist in equiUbtium with mono- and ttialkylboranes and cannot be prepared in a state of high purity by the reaction of two equivalents of an alkene with borane (35—38). Nevertheless, such mixtures can be used for hydroboration if the products are acceptable for further transformations or can be separated (90). When pure primary dialkylboranes are required they are best prepared by the reduction of dialkylhalogenoboranes with metal hydrides (91—93). To avoid redistribution they must be used immediately or be stabilized as amine complexes or converted into dialkylborohydtides. 

Other convenient routes to carboranes, selected from the growing number of recently reported syntheses, are as follows. Monocarbon carboranes can be prepared in good yield by the transition-metal catalysed hydroboration of alkenes followed by thermal rearrangement of the intermediate product, c.gP" ... 

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