Historical developments isomerization

Catalytic reactions of hydrocarbons over zeolites are reviewed. The historical development of various mechanistic proposals, particularly of the carbonium ion type, is traced. In spite of numerous catalytic, spectroscopic, and structural studies which have been reported concerning the possible roles of Bronsted acid, Lewis acid, and cationic sites, it still is not possible to formulate a comprehensive mechanistic picture. New activity and product data for cumene cracking and isotope redistribution in deuterated benzenes over Ca-and La-exchanged Y zeolites is presented. Cracking of the isomeric hexanes over alkali metal-exchanged Y and L zeolites has been studied. This cracking is clearly radical rather than carbonium-ion in nature but certain distinct differences from thermal cracking are described. 

Some of the forms of isomerism have little more than historic interest now, as their significance has diminished with the rise in physical methods that makes their identification and origins routine, and no longer involves the demanding experiments of an earlier era to probe their form. Nevertheless, some remain important, and others at least give a flavour of the historical development of the field, and this deserves a brief discussion. Constitutional isomers are characterized by species of the same empirical formula (which was able to be determined at an early date in the development of the field) but clearly different physical properties associated with different atom connectivity. 

The [Co(CN)5]3 complex is an effective catalyst for some reactions, particularly the isomerization of alkenes. Newer and more efficient catalysts have been developed for some of the processes, but the catalytic behavior of the pentacyanocobalt(II) ion is also significant from a historical perspective. In reactions such as that shown in Eq. (22.10), two Co2+ ions increase one unit in oxidation state, instead of the more common situation in which one metal ion increases by two units in oxidation state. The cobalt complex also reacts with CIT3I, Cl2, and H202, which are indicated as X-Y in the equation... 

Until recently, the phenomenon of chirality has been better known as optical isomerism, and configurational isomers that are enantiomers were referred to as optical antipodes. The reasons for this are mainly historical. It was discovered early in the nineteenth century that many compounds, whether solid, liquid, or gas, have the property of rotating the plane of polarization of polarized light and can be said to be optically active. A satisfactory explanation of the origin of optical activity came much later and developed in its modern form from the classic researches of Louis Pasteur, and from the concept of the three-dimensional carbon atom expressed independently by J. H. van t Hoff and J. A. Le Bel.2... 

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