Catalysis historical aspects

Discuss the historical aspects of organometallic compound toxicity, including organoarsenicals used as pharmaceutical agents, gasoline antiknock additives, and compounds used in applications such as catalysis and chemical synthesis. 

As the historic aspects of the chemistry of group 10 metal-metal bond have been excellently summarized in the textbook by Cotton et al. [2], major effort will be delivered on the latest developments in the last decade (2005-2014). Due to the fact that this lOyears witnessed an explosion of the field and an extremely large body of works has been reported in this time (a search of Cambridge Structural Database (CSD version 03/2014) with key word M-M, where M and M is an arbitrary group 10 met2d, resulted in over 1000 hits published after 2005 ), a comprehensive coverage of the literature is impracticable. Instead, representative synthesis, structural properties, reactivity, as well as applications in catalysis of these compounds will be focused on. 

The synthesis of hydrocarbons from CO hydrogenation over transition metals is a major source of organic synthetic chemicals and fuels. The Fischer-Ttopsch (FT) reaction, which is directed to the production of hydrocarbons from syngas, implies the polymerisation of-CHx entities and carbon-carbon bond formation is required. The historical achievements have been revised on several occasions see for instance, the reviews by Vannice,2 Schulz3 and the special issue of Catalysis TodayA devoted to FT. Also, a synopsis of the main recent industrial developments has been presented by Adesina.5 Furthermore, the recent edition of Topics in Catalysis6 should be mentioned, where different aspects of the reaction mechanism, surface reconstruction of active surfaces, improved reactors and optimisation of catalyst preparations have been treated by various specialists, scientists and engineers. 

This system has its historical background in physical organic chemistry and the kinetic aspects are the subject of a detailed review by SeemarL In essence, this is a special application of the rapid-equilibrium assumption. The Curtin-Hammett conditions and their consequences also are relevant to inorganic systems, and this has been recognized especially in the area of stereoselective catalysis. 

Initially, electrochemical methods were restricted to rather conducting media (solvents with large dielectric constants, large ionic strength), because of problems related to a precise control of an electrode-solution potential difference. Since the rapid development of ultramicroelectrodes in the past decade, this is no more the case, and electrochemistry in solvents of low dielectric constants (arenes, alkanes,efo) or in the absence of deliberately added electrolytes is feasible routinely. Both the theoretical and experimental aspects of such unconventional electrochemistries are now well mastered and the techniques ready for use and application. We have no doubt that the breaking of these historical frontiers of electrochemistry will allow a rich harvest of mechanistic studies performed under conditions that may now approach those used in homogeneous reactions and in catalysis. 

This chapter presents an overview of the different aspects of catalysis as a science, and aims to provide a general background to the reader. In order to understand catalysis as it is today, it is important to have a sense of its historic origin, and of developments in related fields such as thermodynamics, kinetics, and chemical engineering. Although catalysis as a chemical reactivity phenomenon was well known in the nineteenth century, the field developed mainly in the twentieth century. 

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