Transition-metal-catalysis

In this chapter we focus on supramolecular chemical reactivity. In particular this means predominantly the role supramolecular chemistry plays in accelerating or understanding chemical reactions. There are close parallels between artificial, abiotic supramolecular reactivity and biochemistry, for example in the study of enzymes, Nature s catalysts - described in Section 2.6. Synthetic catalysts can both model natural ones and allow the design of new, different kinds of reactions. Supramolecular catalysis sits somewhere between chemical catalysis (transition metal and organocatalysis) and biology. Some considerations within various kinds of catalysis are summed up in the chart shown in Figure 12.1. 

Chemisorption is vital in catalysis. Transition metals such as Fe, Pd, Pt, Ir, Ni, Co, Cr, Mn, Ti, Hf, Zr, V, Nb, Mo, W, Ru, and Os have the ability to chemisorb simple molecules such as 02, CO, H2, C02, C2H4, and N2 [24,25,27], However, if chemisorption is very strong, the catalytic sites are blocked. Therefore, it is necessary that an intermediate between weak chemisorption, when there is no reaction, and strong chemisorption, when the sites are blocked [24,25], is available. In this sense, the first d-block metals form especially stable surface bonds, while the noble metals form weak bonds. These properties are unfavorable to catalysis. Hence, the best metallic catalysts are in between these two groups [27],... 

In heterogeneous catalysis, transition metal nanoparticles are supported on different substrates and are utilized as catalysts for different reactions [57], such as hydrogenations and enantioselective synthesis of organic compounds [58], oxidations and epoxidations [59], and reduction and decomposition [57],... 

Keywords Catalysis Transition metals Radicals Electron transfer Crosscoupling Addition Cyclization... 

In the context of future prospects in catalysis, transition metal complexes seem to provide a particularly diverse source of useful Lewis acids. Although the structural features of these complexes were not discussed extensively in this chapter, ti -bonding seems unique to these complexes and warrants further exploration. 

Ch. M. Starks, Ch. L. Liotta, M. Hal-pern, Phase Transfer Catalysis Fundamentals, Applications, and Industrial Perspectives, Chapman and Hall, New York, 1994. Specifically Chapter 13 Phase transfer catalysis - transition metal cocatalyzed reactions, p. 594. 

The composition and chemical state of the surface atoms or molecules are very important, especially in the field of heterogeneous catalysis, where mixed-surface compositions are common. This aspect is discussed in more detail in Chapter XVIII (but again see Refs. 55, 56). Since transition metals are widely used in catalysis, the determination of the valence state of surface atoms is important, such as by ESCA, EXAFS, or XPS (see Chapter VIII and note Refs. 59, 60). 

The microscopic understanding of tire chemical reactivity of surfaces is of fundamental interest in chemical physics and important for heterogeneous catalysis. Cluster science provides a new approach for tire study of tire microscopic mechanisms of surface chemical reactivity [48]. Surfaces of small clusters possess a very rich variation of chemisoriDtion sites and are ideal models for bulk surfaces. Chemical reactivity of many transition-metal clusters has been investigated [49]. Transition-metal clusters are produced using laser vaporization, and tire chemical reactivity studies are carried out typically in a flow tube reactor in which tire clusters interact witli a reactant gas at a given temperature and pressure for a fixed period of time. Reaction products are measured at various pressures or temperatures and reaction rates are derived. It has been found tliat tire reactivity of small transition-metal clusters witli simple molecules such as H2 and NH can vary dramatically witli cluster size and stmcture [48, 49, M and 52]. 

First, the use of water limits the choice of Lewis-acid catalysts. The most active Lewis acids such as BFj, TiQ4 and AlClj react violently with water and cannot be used However, bivalent transition metal ions and trivalent lanthanide ions have proven to be active catalysts in aqueous solution for other organic reactions and are anticipated to be good candidates for the catalysis of aqueous Diels-Alder reactions. 

Inspired by the many hydrolytically-active metallo enzymes encountered in nature, extensive studies have been performed on so-called metallo micelles. These investigations usually focus on mixed micelles of a common surfactant together with a special chelating surfactant that exhibits a high affinity for transition-metal ions. These aggregates can have remarkable catalytic effects on the hydrolysis of activated carboxylic acid esters, phosphate esters and amides. In these reactions the exact role of the metal ion is not clear and may vary from one system to another. However, there are strong indications that the major function of the metal ion is the coordination of hydroxide anion in the Stem region of the micelle where it is in the proximity of the micelle-bound substrate. The first report of catalysis of a hydrolysis reaction by me tall omi cell es stems from 1978. In the years that... 

The development of methods for aromatic substitution based on catalysis by transition metals, especially palladium, has led to several new methods for indole synthesis. One is based on an intramolecular Heck reaction in which an... 

Addition of HCN to unsaturated compounds is often the easiest and most economical method of making organonitnles. An early synthesis of acrylonitrile involved the addition of HCN to acetylene. The addition of HCN to aldehydes and ketones is readily accompHshed with simple base catalysis, as is the addition of HCN to activated olefins (Michael addition). However, the addition of HCN to unactivated olefins and the regioselective addition to dienes is best accompHshed with a transition-metal catalyst, as illustrated by DuPont s adiponitrile process (6—9). 

Transition-Metal Catalyzed Cyclizations. o-Halogenated anilines and anilides can serve as indole precursors in a group of reactions which are typically cataly2ed by transition metals. Several catalysts have been developed which convert o-haloanilines or anilides to indoles by reaction with acetylenes. An early procedure involved coupling to a copper acetyUde with o-iodoaniline. A more versatile procedure involves palladium catalysis of the reaction of an o-bromo- or o-trifluoromethylsulfonyloxyanihde with a triaLkylstaimylalkyne. The reaction is conducted in two stages, first with a Pd(0) and then a Pd(II) catalyst (29). 

G. N. Schrauzer, ed.. Transition Metals In Homogeneous Catalysis, Marcel Dekker, Inc., New York, 1971. 

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 ... 

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. 

The /n j -I,4-polybutadiene made by transition-metal catalysis (112,113) is a resin-like material that has two melting temperatures, 50 and I50°C. 

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