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General Scope and Applications

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. [Pg.491]

In catalytic conversions of (organo)silicon compounds only the hydrosilylation is a well-known process of industrial importance [1-5]. However, since 1985 other reactions of silicon compounds catalyzed by transition metal complexes have been revealed and spectacularly developed. Most of them occur via a mechanism involving metal-silicon and metal-hydrogen bonds, only occasionally accompanied by (or sided) metal-carbon bonds. [Pg.491]

This chapter presents the hydrosilylation processes as well as the main types of reactions related to hydrosilylation (except double silylation) in which intermediates with metal-silicon bonds (i. e., silicometallics vs. organometallics) play a decisive role with mechanistic implications for both new and well-known catalytic reactions leading to formation of organosilicon compounds [6]. Double silylation (bissilylation) of unsaturated organic compounds has recently been reviewed comprehensively [7]. [Pg.491]

A recent detailed theoretical study of the platinum-catalyzed hydrosilylation of ethylene [15] led to a conclusion that this process proceeds through the Chalk-Harrod mechanism. The rate-determining step in this mechanism is the isomerization of the Pt(silyl)(alkyl) complex formed by ethylene insertion into the Pt-H bond, and the activation barrier of this step is 23 kcal moP for R = Me and -26 kcal mol for R = Cl). In the modified Chalk-Harrod mechanism, however, the rate-determining step is ethylene insertion into the Pt-SiRa bond and its barrier is 44 kcal moP for R = Me and 60 kcal moP for R = Cl. [Pg.493]

The Chalk-Harrod mechanism has been widely accepted with various modifications to account for the hydrosilylation of other multiple bonds (C=C), C=0, C=N), homogeneously catalyzed by various metal complexes. [Pg.493]


The scope and applications of stereoelecttonic concepts have increased so dramatically in the recent decades that providing a comprehensive coverage of this ever-expanding field is impossible within the confines of this book. This chapter will aim to illustrate the generality of stereoelectronic concepts, their interplay with other factors and their broad applicability to different areas of chemistry, biochemistry and materials science. We will provide examples of how recognizing the orbital interactions ability to play many different roles and serve many different purposes has led to the discovery of practically useful chenucal processes. [Pg.275]

The existence of an OSHA regulation does not mean that it applies to every employer. It is important to review the scope and application section of a regulation to ensure how it applies in a given environment. The hazard communication standard is unique in one respect from other regulations in that it has specific target audiences, to include manufacturers, importers, and employers (schools). The scope and application section of the hazard communication standard is contained in 29 CFR 1910.1200(b). The general information is as follows ... [Pg.198]

In this review, different approaches to construct NN potential-energy surfaces have been discussed. Many successful applications already exist, mostly for molecular but also for a few condensed systems. Nevertheless, NN potentials are rather new tools in computational chemistry and although a lot of progress has been made, still significant further methodical developments are necessary to extend their scope and applicability. Therefore, it will take some time before NN potentials may become general purpose potentials for atomistic simulations. However, for certain problems, like low-dimensional PESs of molecular systems or high-dimensional PESs of extended systems with a limited chemical complexity, NN potentials could become a serious alternative to conventional empirical potentials in the next years. [Pg.35]

Bowler, D.T. General systems thinking its scope and applicability. Elsevier, Amsterdam (1981)... [Pg.276]

Interestingly, the Nicolaou s concept of employing IBX to the construction of amino sugars as depicted below is very general in scope and applicable to a variety of carbohydrate building blocks including allylic alcohols (Scheme 14). [Pg.370]

This field is very large and a detailed study of the subject is beyond the scope of this handbook. We will limit our discussions to the area of this subject that relates to the control of a.c. motors and attempt to identify the different solid-state devices that have been developed and their application in the control of a.c. motors. ()nly the more common circuits and configurations are discussed. The brief discussion of the subject provided here, however, should help the reader to understand this subject in general terms and to use this knowledge in the field of a.c. motor controls to achieve from a soft start to a very precise speed control and, more importantly, to conserve the energy of the machine which would be wasted otherwise. For more details of. statie controllers see the Further reading (Sr. nos. 2, 4., 5, 8 and 12) at the end of the chapter. To... [Pg.111]

Part 2, Model Chemistries, provides an in-depth examination of the accuracy, scope of applicability and other characteristics and trade-offs of all of the major well-defined electronic structure models. It also gives some general recommendations for selecting the best model for investigating a particular problem. [Pg.316]

In general, physical methods have been used to study tautomerism more successfully than chemical methods, and, of the physical methods, those involving measurements of basicities and ultraviolet spectra are the most important, followed by those involving measurement of infrared and proton resonance spectra. An attempt is made here to delineate the scope and to indicate the advantages and disadvantages of the various methods. A short review by Mason of the application of spectroscopic methods appeared in 1955. Recently a set of reviews on the applications of physical methods to heterocyclic chemistry has appeared, which treats incidentally the determination of tautomeric structure. [Pg.325]

Among the many chiral Lewis acid catalysts described so far, not many practical catalysts meet these criteria. For a,/ -unsaturated aldehydes, Corey s tryptophan-derived borane catalyst 4, and Yamamoto s CBA and BLA catalysts 3, 7, and 8 are excellent. Narasaka s chiral titanium catalyst 31 and Evans s chiral copper catalyst 24 are outstanding chiral Lewis acid catalysts of the reaction of 3-alkenoyl-l,2-oxazolidin-2-one as dienophile. These chiral Lewis acid catalysts have wide scope and generality compared with the others, as shown in their application to natural product syntheses. They are, however, still not perfect catalysts. We need to continue the endeavor to seek better catalysts which are more reactive, more selective, and have wider applicability. [Pg.48]


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