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Chapter 9

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Yogesh
Indian Institute of Technology (IIT) Bombay, Mumbai
Chemical Engineering

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Unit 9 Objectives After studying this Unit, you will be able to appreciate the postulates of Werner s theory of coordination compounds; know the meaning of the terms: coordination entity, central atom/ ion, ligand, coordination number, coordination sphere, coordination polyhedron, oxidation number, homoleptic and heteroleptic; learn the rules of nomenclature of coordination compounds; write the formulas and names of mononuclear coordination compounds; define different types of isomerism in coordination compounds; understand the nature of bonding in coordination compounds in terms of the Valence Bond and Crystal Field theories; learn the stability of coordination compounds; appreciate the importance and applications of coordination compounds in our day to day life. 9.1 Werner s Werner s Theory of Coordination Compounds Coor dination Coordination Compounds Coordination Compounds are the backbone of modern inorganic and bio inorganic chemistry and chemical industry. In the previous Unit we learnt that the transition metals form a large number of complex compounds in which the metal atoms are bound to a number of anions or neutral molecules. In modern terminology such compounds are called coordination compounds. The chemistry of coordination compounds is an important and challenging area of modern inorganic chemistry. New concepts of chemical bonding and molecular structure have provided insights into the functioning of vital components of biological systems. Chlorophyll, haemoglobin and vitamin B 12 are coordination compounds of magnesium, iron and cobalt respectively. Variety of metallurgical processes, industrial catalysts and analytical reagents involve the use of coordination compounds. Coordination compounds also find many applications in electroplating, textile dyeing and medicinal chemistry. Alfred Werner (1866-1919), a Swiss chemist was the first to formulate his ideas about the structures of coordination compounds. He prepared and characterised a large number of coordination compounds and studied their physical and chemical behaviour by simple experimental techniques. Werner proposed the concept of a primary valence and a secondary valence for a metal ion. Binary compounds such as CrCl3, CoCl2 or PdCl2 have primary valence of 3, 2 and 2 respectively. In a series of compounds of cobalt(III) chloride with ammonia, it was found that some of the chloride ions could be precipitated as AgCl on adding excess silver nitrate solution in cold but some remained in solution.

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