Course Objectives:
The course aims to make the students explain about the various methods of determination of stability constants, to enable the students to learn about kinetics and reaction mechanism of transition metal complexes, and to acquaint the students with the nature of metal-ligand bonding in coordination compounds on the basis of Molecular Orbital Theory.
Course Outcomes (COs):
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On completion of this course, the students will be able to- CO1-determine the stability constants of complexes by various methods. CO2-predict kinetics and mechanism of ligand substitution reactions in octahedral and square planer complexes CO3-apply the concept of trans effect to identify and synthesize cis and trans isomers of square planar complexes CO4-discuss the inner sphere and outer sphere reaction mechanisms CO5-construct molecular orbital diagrams depicting σ- and π-bonding of complexes using the fundamental knowledge of quantum mechanics CO6– explain basic principles of angular overlap model and types of bonding in octahedral complexes. |
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Thermodynamic and kinetic stability, stepwise and overall formation constants, factors affecting stability of complexes, determination of the stability constants of complexes by pH-metric method, ion exchange method, spectrophotometric method and polarographic method, determination of the composition of complexes by Job’s method (method of continuous variation), mole ratio method, slope-ratio method.
Kinetics of substitution reactions in octahedral complexes, acid hydrolysis(SN1 mechanism), factors affecting acid hydrolysis and base hydrolysis, conjugate base mechanism (SN1cB mechanism), direct and indirect evidence in favor of conjugate mechanism, anation reactions, reactions without metal ligand bond cleavage, Berry pseudorotation.
Self-Study-Ligand Substitution Reactions-patterns of reactivity, classification of mechanisms- associative, dissociative and interchange mechanism of substitution, energy profile of reaction transition states, inert and labile complexes.
Trans effect, theories of trans effect and its uses, mechanism of substitution in square planar complexes, factors affecting substitution reactions in square planar complexes, Swain Scott equation, cis-trans isomerization.
Redox Reactions - classification, mechanism of one electron transfer reaction- outer sphere type reactions, cross reactions and Marcus-Hush theory (qualitative treatment), inner sphere type reactions, two electron transfer reaction (brief idea).
Ligand Field Theory- An introduction, molecular orbital diagrams of some simple polyatomic molecules like BeH2, H2O, NH3, Walsh diagrams.
LCAO approximation, σ-only molecular orbital energy levels for octahedral, tetrahedral and square planar complexes.
Molecular orbital energy levels for octahedral, tetrahedral and square planar complexes containing π-bonds, effect of π-bonding. Experimental evidence for π-bonding- crystallography and infra-red spectroscopy.
Angular Overlap Model- principle, σ- and π- bonding in octahedral complexes.
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