Transition metal complexes catalysis

Olefin Hydroformylation (The Oxo Process). One of the most important iadustrial applications of transition-metal complex catalysis is the hydroformylation of olefins (23), ihusttated for propjdene ... 

Conversely, other processes are totally original. This is especially encountered when the electrochemical act is associated with a transition metal complex catalysis. These methods have the advantage of affording the organozinc compound synthesis under simple and mild conditions that are compatible with the presence of reactive functional groups on the substrate. Importantly, these procedures are reproducible and can be run by any chemist. Besides, the preparation from a few millimoles to tens of millimoles of the organometallic compound is easy at the laboratory scale. 

Catalysis in liquid-liquid biphasic systems has developed recently into a subject of great practical interest because it provides an attractive solution to the problems of separation of catalysts from products and of catalyst recycle in homogeneous transition metal complex catalysis. Two-phase systems consist of two immiscible solvents, e.g., an aqueous phase or another polar phase containing the catalyst and an organic phase containing the products. The reaction is homogeneous, and the recovery of the catalyst is facilitated by simple phase separation. 

In contrast to the conventional methods of cycloaddition, capable of forming only one type of product, the reactions catalysed by metal complexes are fairly flexible. This versatility offers numerous possibilities for elaborating a number of methods for the preparation of structurally diverse structures. However, there is still no consistent theory for transition metal complex catalysis which enables one to predict which catalyst and/or conditions are to be employed for the desired transformation. Results are often achieved through intuition and not reasoning. However, who would dare to negate the usefulness of tools like intuition and mere luck if they produce spectacular results like those met in the area of transition metal catalysis "... 

Phase-transfer catalysis (PTC) is the most widely used method for solving the problem of the mutual insolubility of nonpolar and ionic compounds. Basic principles, synthetic uses, industrial applications of PTC, and its advantages over conventional methods are well documented [1-3]. PTC has become a powerful and widely accepted tool for organic chemists due to its efficiency, simplicity, and cost effectiveness. The main merit of the method is its universality. It may be applied to many types of reactions involving diverse classes of compounds. An important feature of PTC is its computability with other methods for the intensification of biphasic reactions (sonolysis, photolysis, microwaving, etc.) as well as with other types of catalysis, in particular, with transition-metal-complex catalysis. Homogeneous metal-complex catalysis under PTC conditions involves the simul-... 

Prior to 1970 the term homogeneous catalysis usually connoted acid-base catalysis, and this is the best understood type of catalysis . Since then, however, homogeneous catalysis has come to mean primarily transition-metal-complex catalysis, which has been the object of intensive research motivated in part by a series of technological accomplishments . ... 

The first industrial processes involving transition-metal-complex catalysis were largely focused on ethyne conversion, but these are no longer important. Many of the present processes involve alkene and CO conversion, including the following ... 

G. W. Parshall, Homogeneous Catalysis, Wiley, New York, 1980. Review of chemistry of transition metal complex catalysis. 

B. C. Gates, J. R. Katzer, G. C. A. Schuit, Chemistry of Catalytic Processes, Chap. 2, McGraw-Hill, New York, 1979. Process chemistry and engineering of transition metal complex catalysis. 

Since Reppe s discovery of the cyclotrimerization of acetylene to benzene in the presence of nickel carbonyl-phosphine complexes, the use of nickel catalysts in many organic transformations has become popular. Transition metal complex catalysis provides many elegant entries to carbon-carbon bond-forming reactions in organic synthesis. One notable example is carbocyclic ring expansion mediated by nickel(O) complexes. ... 

The area of early-late transition metal complex catalysis has been reviewed recently [40]. While there is an ever-growing number of studies in this field, a conclusive and unambiguous example for cooperativity of the two M-M -bonded metal centers is still lacking. 

There are only a few weU-documented examples of catalysis by metal clusters, and not many are to be expected as most metal clusters are fragile and fragment to give metal complexes or aggregate to give metal under reaction conditions (39). However, the metal carbonyl clusters are conceptually important because they form a bridge between catalysts commonly used in solution, ie, transition-metal complexes with single metal atoms, and catalysts commonly used on surfaces, ie, small metal particles or clusters. 

W. A. Nugent and J. M. Mayer, Metal-Eigand Multiple Bonds The Chemistry of Transition Metal Complexes Containing Oxo, Nitrido, Imido, Jilkylidene, orJilkylidyne Eigands,Jolm. Wiley Sons, Inc., New York, 1988. Contains electronic and molecular stmcture, nmr, and ir spectroscopy, reactions, and catalysis. 

G. W. ParshaH, Homogeneous Catalysis The applications and Chemistry of Catalysis by Soluble Transition Metal Complexes,Johm. Wiley Sons, Inc., New York, 1980, 240 pp. An excellent treatment of catalysis by coordination compounds. 

Stable transition-metal complexes may act as homogenous catalysts in alkene polymerization. The mechanism of so-called Ziegler-Natta catalysis involves a cationic metallocene (typically zirconocene) alkyl complex. An alkene coordinates to the complex and then inserts into the metal alkyl bond. This leads to a new metallocei e in which the polymer is extended by two carbons, i.e. 

Catalytic, enantioselective cyclopropanation enjoys the unique distinction of being the first example of asymmetric catalysis with a transition metal complex. The landmark 1966 report by Nozaki et al. [1] of decomposition of ethyl diazoacetate 3 with a chiral copper (II) salicylamine complex 1 (Scheme 3.1) in the presence of styrene gave birth to a field of endeavor which still today represents one of the major enterprises in chemistry. In view of the enormous growth in the field of asymmetric catalysis over the past four decades, it is somewhat ironic that significant advances in cyclopropanation have only emerged in the past ten years. 

Many transition metal complexes dissolve readily in ionic liquids, which enables their use as solvents for transition metal catalysis. Sufficient solubility for a wide range of catalyst complexes is an obvious, but not trivial, prerequisite for a versatile solvent for homogenous catalysis. Some of the other approaches to the replacement of traditional volatile organic solvents by greener alternatives in transition metal catalysis, namely the use of supercritical CO2 or perfluorinated solvents, very often suffer from low catalyst solubility. This limitation is usually overcome by use of special ligand systems, which have to be synthesized prior to the catalytic reaction. 

Since no special ligand design is usually required to dissolve transition metal complexes in ionic liquids, the application of ionic ligands can be an extremely useful tool with which to immobilize the catalyst in the ionic medium. In applications in which the ionic catalyst layer is intensively extracted with a non-miscible solvent (i.e., under the conditions of biphasic catalysis or during product recovery by extraction) it is important to ensure that the amount of catalyst washed from the ionic liquid is extremely low. Full immobilization of the (often quite expensive) transition metal catalyst, combined with the possibility of recycling it, is usually a crucial criterion for the large-scale use of homogeneous catalysis (for more details see Section 5.3.5). 

These advantages notwithstanding, the proportion of homogeneous catalyzed reactions in industrial chemistry is still quite low. The main reason for this is the difficulty in separating the homogeneously dissolved catalyst from the products and by-products after the reaction. Since the transition metal complexes used in homogeneous catalysis are usually quite expensive, complete catalyst recovery is crucial in a commercial situation. 

In comparison with traditional biphasic catalysis using water, fluorous phases, or polar organic solvents, transition metal catalysis in ionic liquids represents a new and advanced way to combine the specific advantages of homogeneous and heterogeneous catalysis. In many applications, the use of a defined transition metal complex immobilized on a ionic liquid support has already shown its unique potential. Many more successful examples - mainly in fine chemical synthesis - can be expected in the future as our loiowledge of ionic liquids and their interactions with transition metal complexes increases. 

Ionic liquids have already been demonstrated to be effective membrane materials for gas separation when supported within a porous polymer support. However, supported ionic liquid membranes offer another versatile approach by which to perform two-phase catalysis. This technology combines some of the advantages of the ionic liquid as a catalyst solvent with the ruggedness of the ionic liquid-polymer gels. Transition metal complexes based on palladium or rhodium have been incorporated into gas-permeable polymer gels composed of [BMIM][PFg] and poly(vinyli-dene fluoride)-hexafluoropropylene copolymer and have been used to investigate the hydrogenation of propene [21]. 

The past fifteen years have seen evidence of great interest in homogeneous catalysis, particularly by transition metal complexes in solution predictions were made that many heterogeneous processes would be replaced by more efficient homogeneous ones. There are two motives in these changes—first, intellectual curiosity and the belief that we can define the active center with... 

A discussion of the different types of solute-solute and solute-solvent interactions acting in homogeneous catalysis by transition metal complexes. E. Cesarotti, R. Ugo and L. Kapan, Coord. Chem. Rev., 1982,43, 275-298 (47). 

Keywords Azolium salts AJ-heterocydic carbenes transition metal complexes asymmetric catalysis... 

Using these procedures, many chiral diaminocarbene-transition metal complexes have been synthesized but only a few of them have been used for asymmetric catalysis. The chiral complexes which were isolated but did not receive any application in asymmetric catalysis, are presented at the end of the chapter. 

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