Olefin catalyzed by transition metal

It is well documented that hydrosilylation of alkyl-substituted terminal olefins catalyzed by transition metal complexes proceeds with high regioselectivity in giving linear hydrosilylation products which do not possess a stereogenic carbon center.2 It follows that the asymmetric synthesis by use of the hydrosilylation of alkyl-substituted... 

Many discoveries changed human life in the last fifty years, and the polymerization of olefins catalyzed by transition metals certainly can be considered among them. At first glance, the job requested to polymerization catalysts seems rather trivial. It consists in the enchainment of monomeric units by insertion of olefins into Mt-P (P = Polymeric chain) bonds. Despite its simplicity and the amount of work by many research groups both in the... 

The direct transfer of carbene from diazocompounds to olefins catalyzed by transition metals is the most straightforward synthesis of cyclopropanes [3,4]. Reactions of diazoesters with olefins have been studied using complexes of several transition metals as catalysts. In most cases trans-isomers are preferably obtained, but the selectivity depends on the nature of the complex. In general the highest trans-selectivity is obtained with copper catalysts and it is reduced with palladium and rhodium complexes. Therefore, the rhodium mesotetraphenylporphyrin (RhTPPI) [5] and [(r 5-C5H5)Fe(CO)2(THF)]BF4 [6] are the only catalysts leading to a preference for the cis-isomer in the reaction of ethyl diazoacetate with styrene. 

Mechanism of Hydrosilylation of Olefins Catalyzed by Transition-Metal Complexes... 

AEROBIC OXYGENATION OF OLEFINS CATALYZED BY TRANSITION-METAL COMPLEXES... 

Hydrogenation of olefins catalyzed by transition metal complexes dissolved in ionic liquid solvents have been reported using rhodium-, and ruthenium- and cobalt-containing catalysts. In these studies it was shown that hydrogenation rates where up to five times higher than the comparable reactions when carried out in propanone. The solubilities of the alkene reagents, TOFs, and product distributions where all strongly influenced by the nature of the anion in the ionic liquid solvent... 

The hydrogenation of olefins catalyzed by transition metals is a very important industrial reaction. The initial step in the catalytic cycle is the addition of H2 to a square planar complex to form an octahedral metal dihydride. There are two possible ways that H2 can approach a d ML4 complex. These are shown in reactions (I) and (2). 

Epoxidation reactions have been widely utilized for over 100 years with peradds, peroxides and, more recently, metal catalysts [7]. However, direct metal-catalyzed aerobic epoxidations are rare and generally require an aldehyde coreductant. In this case, the metal is proposed to catalyze radical formation (A-C, Scheme 5.2) followed by O2 insertion to form acyl peroxide D. Metal-catalyzed aerobic oxidation of aldehydes to peradds has previously been observed [8]. With the formation of species D, either an outer-sphere path similar to a peracid-type oxidation occurs (Path 1) or an inner-sphere metal-catalyzed oxidation in which the metal-based oxidant and substrate interact during oxygen transfer (Path 2 or 3). Mu-kaiyama and coworkers were the first to report an aerobic epoxidation of olefins catalyzed by transition metals using either a primary alcohol or an aldehyde as coreductants [9]. The role of the metal was probed through parallel studies of peracid and metal-catalyzed epoxidations of 2 which yielded different stereochemical outcomes. Therefore, a metal-centered mechanism for olefin epoxidation was proposed which implicates an oxygenase system. Path 2 or 3 (Table 5.1) [10]. 

Olefin epoxidation by alkyl hydroperoxides catalyzed by transition metal compounds occupies an important place among modern catalytic oxidation reactions. This process occurs according to the following stoichiometric equation ... 

This reaction is invariably catalyzed by transition metal compounds and its mechanism is of special interest. The first explanation for this transformation is based on the so-called pairwise mechanism , in which two olefins coordinate to a transition metal center to form a transient cyclobutane-like intermediate [2], However, this idea was later replaced... 

The Metathesis of Unsaturated Hydrocarbons Catalyzed by Transition Metal Compounds J. C. Mol and J. A. Moulijn One-Component Catalysts for Polymerization of Olefins Yu. Yermakov and V. Zakharov The Economics of Catalytic Processes J. Dewing and D. S. Davies Catalytic Reactivity of Hydrogen on Palladium and Nickel Hydride Phases... 

Abstract The applications of hybrid DFT/molecular mechanics (DFT/MM) methods to the study of reactions catalyzed by transition metal complexes are reviewed. Special attention is given to the processes that have been studied in more detail, such as olefin polymerization, rhodium hydrogenation of alkenes, osmium dihydroxylation of alkenes and hydroformylation by rhodium catalysts. DFT/MM methods are shown, by comparison with experiment and with full quantum mechanics calculations, to allow a reasonably accurate computational study of experimentally relevant problems which otherwise would be out of reach for theoretical chemistry. 

The Metathesis of Unsaturated Hydrocarbons Catalyzed by Transition Metal Compounds J. C. Mol and J. A. Moulijn One-Component Catalysts for Polymerization of Olefins... 

As mentioned above, catalytic oxidation of olefins via coordination catalysis with an intermediate such as LnM (olefin) 02 seemed an attractive possibility, and Collman s group (45) tentatively invoked such catalysis in the 02-oxidation of cyclohexene to mainly 2-cyclo-hexene-1-one promoted by IrI(CO)(PPh3)2, a complex known to form a dioxygen adduct. Soon afterwards (4, 46, 47) such oxidations involving d8 systems generally were shown to exhibit the characteristics of a radical chain process, initiated by decomposition of hydroperoxides via a Haber-Weiss mechanism, for example Reactions 10 and 11. Such oxidations catalyzed by transition-metal salts such as... 

Olefins usually give the terminal product. The reaction is catalyzed by transition metal complexes, e.g., H2Ptd6 or RhCl(PPh3)3 it may involve the oxidative addition of Si—H bonds across a transition metal as shown in Fig. 8-2. 

Of the three possible substrates, thiophene, benzo[ ]thiophene, and dibenzo[, thiophene, benzo[ ]thiophene is the most easily hydrogenated to the dihydro derivative this is ascribable to the more pronounced olefinic character of the C(2)-C(3) double bond in benzo[, ]thiophene as compared to that in thiophene. There is no example in the literature of the hydrogenation of dibenzothiophene either to the tetrahydro or the hexahydro stage. The hydrogenation of benzol ]thiophene is catalyzed by transition metals such as Ru, Os, Rh, and Ir. An excellent overview of homogeneous catalytic hydrogenation of thiophenic substrates has been presented recently <2004JOM (689)4277>. 

The compehtion of one-electron pathways is sometimes detectable in the epoxidations catalyzed by transition metal catalysts [67]. However, in the epoxidahon of unhindered olefins on TS-1, the typical radical products are below the detection limits. Their presence could no longer be neglected when the rate of epoxidation is so slow as to become comparable to that of homolytic side reactions, for example with bulky olefins (see also Section 18.11). It is possible that, within these limits only, the epoxide is produced in part through the addition of a radical peroxy intermediate to the double bond [68, 69]. Even so, a homolytic pathway has again been proposed as a generally vahd epoxidation mechanism [7]. 

Recent Developments in Theoretical Organometallic Chemistry, 15, 1 Redistribution Equilibria of Organometallic Compounds, 6, 171 Redistribution Reactions of Transition Metal Organometallic Complexes, 23, 9S Redistribution Reactions on Silicon Catalyzed by Transition Metal Complexes, 19, 213 Remarkable Features of (t) -Conjugated Diene) zirconocene and -hafnocene Complexes, 24, 1 Selectivity Control in Nickel-Catalyzed Olefin Oligomerization, 17, lOS Silyl, Germyl, and Stannyl Derivatives of Azenes, N H Part I. Derivatives of Diazene, N3H2, 23, 131... 

Over the last 50 years numerous reactions of organic compounds catalyzed by transition metal complexes have been developed (e. g., olefin oxidation -Wacker Process, hydroformylation, carbonylation, hydrogenation, metathesis, Ziegler-Natta polymerization and oligomerization of olefins) in which the reactivity of metal-carbon bonds in the active intermediate (organometallics) is crucial. 

C. L. Hill, R. B. Brown Jr., Sustained epoxidation of olefins by oxygen donors catalyzed by transition metal-substituted polyoxometalates, oxidatively resistant inorganic analogs of metalloporphyrins, J. Am. Chem. Soc. 108 (1986) 536. 

Carbon-carbon bond formation by olefin metathesis catalyzed by transition metal ligands (Grubbs (A) Schrock (B) Hermann (C) Tebbe (D) Nugent (E). 

Formation of C-C Bonds by Addition to Olefinic Double Bonds Catalyzed by Transition Metals... 

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