Butadiene complexes with palladium

Bis(butadiene) complexes, with tantalum, 5, 173 Bis(z-butanethiolato) complexes, with bis-Cp Ti(IV), 4, 601 Bis(calixarene) complexes, as organic molecule hosts, 12, 799 Bis(carbene) complexes with gold(I), 2, 287-288 with manganese, 5, 780, 5, 826 with mercury, 2, 429 with palladium, 8, 230 with silver , 2, 206... 

Unlike nickel Catalysts, palladium complexes do not catalyze the homo-cyclization reaction to give CDT or COD. The difference seems to be due to a different degree of hydride shift and atomic volume. With palladium catalysts, the hydride shift is easier, and hence linear oligomers are formed. The characteristic reaction catalyzed by palladium is the cocyclization of two moles of butadiene with one-hetero atom double bonds such as C=N and C=0 bonds to give six-membered rings with two vinyl groups (19) ... 

If the unsaturated hydrocarbon is a diene, both double bonds may coordinate to palladium ). (Diene)palladium(II) complexes have been isolated and characterized. For example, 2 and 3 are stable complexes in which both double bonds are coordinated to the metal10. Conjugated dienes constitute a special case and although /j4-diene complexes, e.g. 4, are postulated as intermediates, they have not yet been isolated. The butadiene complex 4 is in equilibrium with the zr-allyl complex 5 in solution, and attempts to isolate the diene complex from this mixture lead to formation of a yellow crystalline complex 511. 

Ceric ammonium nitrate promoted oxidative addition of silyl enol ethers to 1,3-butadiene affords 1 1 mixtures of 4-(/J-oxoalkyl)-substituted 3-nitroxy-l-butene and l-nitroxy-2-butene27. Palladium(0)-catalyzed alkylation of the nitroxy isomeric mixture takes place through a common ij3 palladium complex which undergoes nucleophilic attack almost exclusively at the less substituted allylic carbon. Thus, oxidative addition of the silyl enol ether of 1-indanone to 1,3-butadiene followed by palladium-catalyzed substitution with sodium dimethyl malonate afforded 42% of a 19 1 mixture of methyl ( )-2-(methoxycarbonyl)-6-(l-oxo-2-indanyl)-4-hexenoate (5) and methyl 2-(methoxycarbonyl)-4-(l-oxo-2-indanyl)-3-vinylbutanoate (6), respectively (equation 12). 

The strong acidity of the proton at the C2 position of a [AMIM] ion has been well recognized 183). This cation can react with palladium complexes to form inactive l,3-dialkylimidazol-2-ylidene palladium complexes 200), as confirmed in a study of the conventional Pd(OAc)2/PPh3/base catalyst in ionic liquids for the telomerization of butadiene with methanol at 85°C 201). 

Finally, a third means of ligand formation from an imidazolium cation, described by Dupont and co-workers, should be mentioned here [34]. They investigated the hydrodimerization/telomerization of 1,3-butadiene with palladium(II) compounds in [BMIM][BF4] and described the activation of the catalyst precursor complex [BMIM]2[PdCl4] by a palladium(lV) compound formed by oxidative addition of the imidazolium nitrogen atom and the alkyl group with cleavage of the C-N bond of the [BMIM] ion, resulting in bis(methyHmidazole) dichloropalladate (Scheme 5.2-5). However, this reaction was only observed in the presence of water. 

Complex compounds with halide bridges are prepared by immediate interaction of unsaturated hydrocarbons with metal salts (Sec. 2.2.4.1). Their examples are classic 7i-complexes of the type 123 which are characteristic for fi 8-metals [75]. Such complexes are also formed by the method of ligand exchange. The bridges of this type are widespread in products of cyclometallation reactions with the use of metal halides (Sec. 2.2.5.1) 371-374, 381, 382 [41,46,48]. An example of such a synthesis is the reaction of arylhydrazones of 2-oxopropionic aldehyde and benzoylformalde-hyde, as well as butadiene-2,3-dione 635, with palladium dichloride, leading (3.71) to dipalladium complexes 636 [88] ... 

Sasaki Y, Inoue Y, Hashimoto H (1976) Reaction of carbon dioxide with butadiene catalysed by palladium complexes. Synthesis of 2-ethylidenehept-5-en-4-olide. J Chem Soc, Chem Commun 605-606... 

Both 1,4- and 1,5-dienes form stable complexes with Pd. For most 1,3-dienes, such as 1,3-butadiene, reaction with Pd° compounds leads to 7r-allyl formation. These reactions are described in Section 7. The coordinated double bonds in palladium diene complexes are reactive toward attack by many nucleophiles, and the resulting chelating alkene palladium alkyls are easily isolated. Many useful reactions of dienes were discovered by Jiro Tsuji in the 1960s and 1970s. These have been recently reviewed in a historical memoir. ... 

Reaction of hydroxylic compounds with butadiene has been studied with palladium compounds. A common feature is the dimerization of butadiene with incorporation of functional groups from alcohols (270). l-Methoxyoctadiene-2,7 was obtained from butadiene and methanol in the presence of Pd(maleic anhydride)(PPh3)2 (273). Complex Pt(PPh3)4 has also been used, although platinum compounds were less effective. Octadienyl esters were obtained from butadiene and acetic acid in the presence of Pd(acac)2 and either PPh3 or P(OPh)3 (294). Palladium complexes were effective for the synthesis of jS,y-unsaturated esters from butadiene, methanol, and CO. The favored mechanism involved addition of a hydropalladium complex to butadiene to give an allylpalladium intermediate (46). 

Alkylation of hydrazine with a, 3-unsaturated carbonyl derivatives or carbonyl derivatives with a leaving group in the p-position provides pyrazole derivatives. For example, treatment of the tosylate (77), obtained from L-serine, with anhydrous hydrazine gives racemic pyrazolidinone (78). It appears that py-razolidinone (78) or one of the intermediates suffers base-catalyzed racemization (equation 32). Starting from P-lactam (79) seven-membered cyclic hydrazine (80) has been formed by ring closure in an unusually high (84%) yield (equation 33). Reaction of ( ir-allyl)palladium complex (81) with dimethyl-hydrazine produces exocyclic diene (82) in a modest (29%) yield, but this is still more efficient than the reaction of 2,3-bis(chloromethyl)butadiene (83) with dimethylhydrazine (equation 34). ... 

There is a notable tendency to form oligomers when acetylenic substances interact with compounds of metals, and this tendency is also shown by butadiene 117) (see Section IV, B,d). This is particularly so with the carbonyls of iron and cobalt, and the oligomerization reactions are favored with nickel 121) and with palladium compounds 113, 122, 123). This phenomenon may be related to the hydropolymerization of acetylenes on metal surfaces, and it may be that such polymerization processes would be better described in terms of ir-complexes. 

Yields are 5-40%. Study of allylic compounds5 and of butadiene6 has led to the following formulation of the complex of butadiene with palladium chloride and the two products obtained on carbonylation ... 

Telomerization reactions, the formation of short oligomers from dienes, represent a very efficient organic transformation with an overall atom economy of 100%, and they have been the subject of intensive research in both academic and industrial laboratories. Complexes of palladium are known to catalyze the reaction of dienes with a variety of nucleophiles. Mechanistically, the reactions are thought to proceed by allyl coordination of two butadiene molecules to a palladium(O) center followed by the formation of a C-C bond. The eight-carbon chain is then attacked by a nucleophile at the terminal or at the 3 position. The reaction usnally leads to a mixture of cis/trans isomers and n- and iio-prodncts. When the nncleophile is methanol, l-methoxyocta-2,7-diene 1 (n-product) is generally the major prodnct, which is a nseful precnrsor for plasticizer alcohols (octanols), solvents, corrosion inhibitors, and monomers for polymerization. ... 

The interpretation of the formation of the Ci3-lactone requires a sequence of mechanistical pathways which are unknown so far in rhodium-catalysis. Two proposals for the mechanism were given in Equation 12. The mechanism of path B is similar to that shown for palladium catalysis. A rhodium Cg-carboxylate complex is formed which under further incorporation of butadiene could yield the lactone. In the mechanism of path A three molecules of butadiene react with the starting rhodium compound forming a C- 2 Chain, which is bound to the rhodium by two n -ally1 systems and one olefinic double bond. Carbon dioxide inserts into one of the rhodium allyl bonds thus forming a C- 3-carboxyl ate complex, which yields the new C-13-lactone. 

Specific examples of the hydrosilylation of dienes are shown in Equations 16.25-16.28. The hydrosilylation of butadiene with Speier s catalyst gives a mixture of mono- and diaddition products, but the hydrosilylation of isoprene forms predominantly 3-methyl-2-butenylsilane, as shown in Equation 16.25. In contrast, triphenylphospliine complexes of palladium generate 2-butenylsilane from a single 1,4-addition of silane to butadiene "... 

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