Catalytic reactions mechanistic classification

Important catalytic reaction concepts include structure sensitivity and insensitivity of reactions, mechanistic classifications (Langmuir-Hinshelwood, Eley-Rideal), the compensation effect, the presence of strongly chemisorbed overlayer, and the roles of structure and bonding modifier additives (promoters). 

A rational classification of reactions based on mechanistic considerations is essential for the better understanding of such a broad research field as that of the organic chemistry of Pd. Therefore, as was done in my previous book, the organic reactions of Pd are classified into stoichiometric and catalytic reactions. It is essential to form a Pd—C cr-bond for a synthetic reaction. The Pd— C (T-bond is formed in two ways depending on the substrates. ir-Bond formation from "unoxidized forms [1] of alkenes and arenes (simple alkenes and arenes) leads to stoichiometric reactions, and that from oxidized forms of alkenes and arenes (typically halides) leads to catalytic reactions. We first consider how these two reactions differ. 

Reactions of another class are catalyzed by Pd(II) compounds which act as Lewis acids, and are treated in Chapter 5 and partly in Chapter 4. From the above-mentioned explanation, the reactions catalyzed by Pd(0) and Pd(II) are clearly different mechanistically. In this book the stoichiometric and catalytic reactions are classified further according to reacting substrates. However, this classification has some problems, viz. it leads to separate treatment of some unit reactions in different chapters. The carbonylation of alkenes is an example. Oxidative carbonylation of alkenes is treated in Chapter 3 and hydrocar-bonylation in Chapter 4. 

Another possible electrocatalytic process is that related to a surface-bound molecule which can give rise to a two-electron reaction. In these conditions, the coupling of the catalytic reaction in the presence of an adequate species in solution can lead to different mechanistic schemes from which the elucidation of the global reaction path is not immediate. This situation matches the behavior of a great number of inorganic catalysts (such polyoxometallates or ion complexes) [86, 98] and biological molecules (enzymes, proteins, oligonucleotides, etc.) [79, 80], for which there is a lack of theoretical basis which enables a clear classification of the different possibilities that can be encountered. 

Classification of Catalytic Reactions Based on Mechanistic Consideration... 

Classification of catalytic reactions based on mechanistic consideration... 

This chapter is intended to focus on catalysis in both thermal and photoinduced electron transfer reactions between electron donors and acceptors by investigating the effects of an appropriate substance that can reduce the activation barrier of electron transfer reactions. It is commonly believed that a catalyst affects the rate of reaction but not the point of equilibrium of the reaction. Thus, a substance is said to act as a catalyst in a reaction when it appears in the rate equation but not in the stoichiometric equation. However, autocatalysis involves a product acting as a catalyst. In this chapter, a catalyst is simply defined as a substance which affects the rate of reaction. This is an unambiguous classification, albeit not universally accepted, including a variety of terms such as catalyzed, sensitized, promoted, accelerated, enhanced, stimulated, induced, and assisted. Both thermal and photochemical redox reactions which would otherwise be unlikely to occur are made possible to proceed efficiently by the catalysis in the electron transfer steps. First, factors that accelerate rates of electron transfer are summarized and then each mechanistic viability is described by showing a number of examples of both thermal and photochemical reactions that involve catalyzed electron transfer processes as the rate-determining steps. Catalytic reactions which involve uncatalyzed electron transfer steps are described in other chapters in this section [66-68]. 

B. CLASSIFICATION OF CATALYTIC REACTIONS BASED ON MECHANISTIC CONSIDERATIONS... 

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