Coordination Chemistry And Organometallic Chemistry

Course Code2875Marks: 100Credits: 4Class Hours: 60Course TitleCoordination Chemistry And Organometallic ChemistryTransition and Inner Transition Elements:Transition elements, main andinner transition elements, their positions in the periodic table, main transition elements: general characteristics, melting and boiling points, variable oxidation states, color of complex ions, magnetism -origin of paramagnetism and diamagnetism, magnetic susceptibility, Curie's law, Curie-Weiss law,techniques of magnetic measurements, Gouy balance, ferromagnetism and antiferromagnetism, lanthanides and actinides: oxidation states, atomic and ionic radii of M3+ions, magnetic properties of M3+ions, lanthanide contraction, chemical reactivity of lanthanides, separation of lanthanide and actinide compounds, comparison between 3d and 4f block elements.1.Concept of Coordination compounds:Coordination compounds, double salts and coordination compounds, coordination sphere, coordination number, ligand types, properties of ligands, nomenclature of coordination compounds, isomerism in coordination compounds –structural isomerism and stereo isomerism, stability: thermodynamic and kinetic stability of coordination compounds, stepwise and overall stability constants, factors affecting the stability of metal complexes. 2.Bonding in Coordination Compounds:Coordination bond, Werner’s coordination postulate, limitations of Werner’s postulate, Sidgwick’s electronic concept, application of EAN rule, limitations of Sidwick’s concept, assumptions of valence bond theory (VBT), hybridization and geometry of complexes, inner orbital and outer orbital octahedral complexes, limitations of VBT, important features of crystal field theory (CFT), orbital splitting and electron spin, factors influencing the magnitude of 10dq, spectrochemical series, high and low spin complexes, crystal field stabilizing energies of dnconfiguration (n = 0 to 10), four and six coordination preferences, magnetic moments, color of transition metal complexes, distortion of octahedral complexes and Jahn-Teller theorem, limitations of CFT, ligand field theory (LFT), molecular orbital theory (MOT), MOT as applied to octahedral complexes, comparison of different theories.3.Reactions and Mechanisms in Coordination Chemistry: Inert and labile ligands,substitution reactions, types of substitution reactions, nucleophilic substitution reactions, association, dissociation and interchange mechanisms, factors affecting the rate of substitution reactions, acid and base hydrolysis reactions, the conjugate base mechanism, stereochemistry of octahedral substitution, substitution in square planar complexes, trans effect –theories of trans effect, uses of trans effect, substitution in tetrahedral complexes, fluxionality in coordination compounds.4.Metal Carbonyls and Nitrosyls:Pi-acid ligands and pi-acid complexes, metal carbonyl and metal nitrosyl complexes, preparation and properties of metal carbonyl and nitrosyl complexes, M-C-O and M-N-O bonding, bridging and terminal COs and NOs, infrared and 13C NMR analysis of carbonyls and nitrosyls, biological role of nitrosyl compound.5.Organometallics and Their Catalytic Aspects:Introduction, general characteristics, ligands in organometallic chemistry, 18-and 16-electron rule, stability of organometallic compounds, classification of organometallic compounds, preparative routes for metal-carbon bond formation, bonding between metal atoms and organic pi systems, structuresof Zeise's salt and ferrocene, 
organometallic reactions –ligand dissociation and substitution, oxidative addition, reductive elimination, carbonyl insertion, homogeneous catalysis, hydrogenation by Wilkinson's catalyst, hydroformylation, heterogeneous catalysis, Ziegler-Nata polymerizations, water gas reactions, Fisher-Tropsch reaction.Books Recommended:1.Inorganic Chemistry, J. E. Huheey, E. A. Keiter, and R. L. Keiter, Harper Collins College Publishers.2.Advanced Inorganic Chemistry, F. A. Cotton, G. Wilkinson, C. A. Murillo and M. Bochmann, John Wiley & Sons, Inc.3.Selected Topics on Advanced Inorganic Chemistry, S. Z. Haider, Students’ Publications.4.Inorganic Chemistry, D. F. Shriver, P. W. Atkins and C. H. Langford, Oxford University Press.5.Kinetics and Mechanism, A. A. Frost and R. G. Pearson, John Wiley & Sons.6.Inorganic Reaction Mechanisms, M. L. Tobe, Thomas Nelson and Sons Ltd