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Alkenes metal carbonyl reaction

However, the pathways for these reactions, particularly in the gas phase, have been only -.rtially characterized. In a wide variety of these reactions, coordinatively unsaturated, highly reactive metal carbonyls are produced [1-18]. The products of many of these photochemical reactions act as efficient catalysts. For example, Fe(C0)5 can be used to generate an efficient photocatalyst for alkene isomerization, hydrogenation, and hydrosilation reactions [19-23]. Turnover numbers as high as 3000 have been observed for Fe(C0)5 induced photocatalysis [22]. However, in many catalytically active systems, the active intermediate has not been definitively determined. Indeed, it is only recently that significant progress has been made in this area [20-23]. [Pg.86]

Hydroxycarbonylation and alkoxycarbonylation of alkenes catalyzed by metal catalyst have been studied for the synthesis of acids, esters, and related derivatives. Palladium systems in particular have been popular and their use in hydroxycarbonylation and alkoxycarbonylation reactions has been reviewed.625,626 The catalysts were mainly designed for the carbonylation of alkenes in the presence of alcohols in order to prepare carboxylic esters, but they also work well for synthesizing carboxylic acids or anhydrides.137 627 They have also been used as catalysts in many other carbonyl-based processes that are of interest to industry. The hydroxycarbonylation of butadiene, the dicarboxylation of alkenes, the carbonylation of alkenes, the carbonylation of benzyl- and aryl-halide compounds, and oxidative carbonylations have been reviewed.6 8 The Pd-catalyzed hydroxycarbonylation of alkenes has attracted considerable interest in recent years as a way of obtaining carboxylic acids. In general, in acidic media, palladium salts in the presence of mono- or bidentate phosphines afford a mixture of linear and branched acids (see Scheme 9). [Pg.188]

Most researchers currently agree that the hydrido mechanism is more common than the alkoxycarbonyl path in the alkoxycarbonylation of alkenes with palladium systems. However, carbalkoxy complexes are putative intermediates in carbonylation reactions giving succinates and polyketone diesters, with metals like Co, Rh, or Pd.137... [Pg.192]

It is important to realize that there is a great deal of overlap in the topics covered in this chapter. For example, the chemistry of metal carbonyls is intimately related to metal alkene complexes, because both types of ligands are soft bases and many complexes contain both carbonyl and alkene ligands. Also, both areas are closely associated with catalysis by complexes discussed in Chapter 22, because some of the best-known catalysts are metal carbonyls and they involve reactions of alkenes. Therefore, the separation of topics applied is certainly not a clear one. Catalysis by metal complexes embodies much of the chemistry of both metal carbonyls and metal alkene complexes. [Pg.739]

Since the early work dealing with Zeise s salt, many complexes have been prepared with the formula [PtL(C2H4)X2], where L = quinoline, pyridine, or ammonia and X=C1 , Br , I, or N()2. Similar compounds have been prepared that contain other alkenes than C2H4. Many of the complexes containing dienes, trienes, and tetraenes as ligands also contain carbonyl ligands. In fact, metal carbonyls are frequently starting complexes from which alkene complexes are obtained by substitution reactions. [Pg.759]

Pettit and coworkers—metal hydride intermediates by weak base attack over Fe carbonyl catalysts. Pettit et al.ls approached the use of metal carbonyl catalysts for the homogeneous water-gas shift reaction from the standpoint of hydroformyla-tion by the Reppe modification.7 In the typical hydroformylation reaction, an alkene is converted to the next higher aldehyde or alcohol through reaction of CO and H2 with the use of a cobalt or rhodium carbonyl catalyst. However, in the Reppe modification, the reduction is carried out with CO and H20 in lieu of H2 (Scheme 6) ... [Pg.125]

Abstract The transition metal mediated conversion of alkynes, alkenes, and carbon monoxide in a formal [2 + 2+1] cycloaddition process, commonly known as the Pauson-Khand reaction (PKR), is an elegant method for the construction of cyclopentenone scaffolds. During the last decade, significant improvements have been achieved in this area. For instance, catalytic PKR variants are nowadays possible with different metal sources. In addition, new asymmetric approaches were established and the reaction has been applied as a key step in various total syntheses. Recent work has also focused on the development of CO-free conditions, incorporating transfer carbonylation reactions. This review attempts to cover the most important developments in this area. [Pg.172]

In a number of classes of systems, the catalytic and other chemical effects of metal ions on reactions of organic and inorganic molecules are generally recognized the catalysis of nucleophilic reactions such as ester hydrolysis the reactions of alkenes and alkynes in the presence of metal carbonyls (8, 9, 69) stereospecific polymerization in the presence of Ziegler catalysts (20, 55, 56) the activation of such small molecules as H2 (37), 02 (13), H202 (13), and possibly N2 (58) and aromatic substitution reactions of metal-cyclopentadienyl compounds (59, 63). [Pg.6]

Reactions of Alkenes and Alkynes in Presence of Metal Carbonyls. Metal carbonyls—e.g., Ni(CO)4, Fe(CO)5, and Co2(CO)s—and hydrocarbonyls— HCO(CO)4 and H2Fe(CO)4—act as catalysts for the transformation of simple unsaturated materials into a wide variety of larger molecules. Perhaps the simplest example is that of hydroformylation (Equation 7). Reppe chemistry... [Pg.7]

The examples chosen in connection with the reactions of alkenes and alkynes in the presence of metal carbonyls illustrate a number of the factors pertinent to the general realm of ligand reactions. [Pg.9]

It was discovered by Roelen in 1938 and is the oldest and largest volume catalytic reaction of alkenes, with the conversion of propylene to butyraldehyde being the mosi important. About 5 million tons of aldehydes and aldehyde derivatives (mostly alcohols) are produced annually making the process the most important industrial synthesis using a metal carbonyl complex as a catalyst. The name hydroformylation arises from the fact that in a formal sense a hydrogen atom and. formyl group are added across a double bond. The net result of the process is extension of (he carbon chain by one and introduction of oxygen into the molecule. [Pg.891]

Numerous synthetically useful carbon-carbon bond-forming reactions are based on the fact that unsaturated hydrocarbon ligands bound to electrophilic transition metal moieties are activated toward addition of nucleophiles. Normally the metal moiety in such complexes is a neutral or cationic metal carbonyl group. Prominent and well-studied examples include [Cr(arene)(CO)3] complexes (covered in Chapter 2.4, this volume),1 [Fe(dienyl)(CO)3]+ complexes (covered in Chapter 3.4, this volume),2 [FeCp(CO)2(alkene)]+ complexes3 and [M(CO) (diene)] complexes.4... [Pg.695]

The range of alkenes that may be used as substrates in these reactions is vast Suitable catalysts may be chosen to permit use of ordinary alkenes, electron deficient alkenes such as a,(3-unsaturated carbonyl compounds, and very electron rich alkenes such as enol ethers. These reactions are generally stereospecific, and they often exhibit syn stereoselectivity, as was also mentioned for the photochemical reactions earlier. Several optically active catalysts and several types of chiral auxiliaries contained in either the al-kene substrates or the diazo compounds have been studied in asymmetric cyclopropanation reactions, but diazocarbonyl compounds, rather than simple diazoalkanes, have been used in most of these studies. When more than one possible site of cyclopropanation exists, reactions of less highly substituted alkenes are often seen, whereas the photochemical reactions often occur predominantly at more highly substituted double bonds. However, the regioselectivity of the metal-catalyzed reactions can be very dependent upon the particular catalyst chosen for the reaction. [Pg.961]

Hydrosilylation reactions catalyzed by iron carbonyl compounds often occur under drastic thermal conditions. Schroeder and Wrighton reported a photocatalyzed reaction oftrialkylsilanes with alkenes in the presence of Fe(CO)5 at low temperatures (0-50 °C) [48]. It is well known that irradiation of mononuclear metal carbonyls leads... [Pg.137]

Carbamoyl or alkoxycarbonyl complexes 87 are obtained by the attack of amines or alkoxides to metal carbonyls. They are important intermediates of carbonylation reactions and undergo insertion of alkene and alkyne. [Pg.22]

Addition of H and CO to alkenes and alkynes catalysed by transition metal complexes is called hydrocarbonylation, and is useful for the syntheses of carboxylic acids, their esters, aldehydes and ketones [1]. Oxidative carbonylation of alkenes and alkynes with Pd(II), treated in Section 11.1.5, differs mechanistically from hydrocarbonylation. Some carbonylation reactions occur at under 1 atm or low pressures, without using a high-pressure laboratory apparatus. Several commercial processes based on hydrocarbonylation have been developed. [Pg.227]


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