Stability, Bonding and Inorganic Reaction Mechanism

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Paper Code: 
CHY 121
Contact Hours: 
60.00
Objective: 

To learn about kinetics and reaction mechanism of transition metal complexes, and the nature of metal-ligand bonding in coordination compounds.

 

11.00
Unit I: 
Stability of Complex ions in Solution

Thermodynamic and kinetic stability, stepwise and overall formation constants, factors affecting stability of complexes. Determination of the stability constants of complexes: pH-metric method, ion exchange method, spectrophotometric method and polarographic method, determination of composition of complexes: Job’s method (method of continous variation), mole ratio method, slope-ratio method.

13.00
Unit II: 
Mechanism of Reactions of Transition Metal Complexes-I

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 favour of conjugate mechanism.  Anation reactions: reactions without metal ligand bond cleavage, Berrys’s pseudo rotation mechanism.

            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.

12.00
Unit III: 
Mechanism of Reactions of Transition Metal Complexes-II

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).

 

12.00
Unit IV: 
Molecular Orbital Theory-I (σ-bonding)

Ligand Field Theory: An introduction, molecular orbital diagrams of some simple polyatomic molecules like BeH2, H2O, NH3, Walsh diagrams: LCAO’s approximation, σ-only molecular orbital energy levels for octahedral, tetrahedral and square planar complexes.

 

12.00
Unit V: 
Molecular Orbital Theory-II (π-bonding)

Molecular orbital energy levels for octahedral, tetrahedral and square planar complexes containing π-bonds, effect of pi-bonding. Experimental evidences for π - bonding: crystallography and Infra red spectroscopy.

Angular Overlap Model: Principles, σ- and π- bonding in octahedral complexes.

 

Essential Readings: 

1.         Inorganic Chemistry; Fifth Edition; D.F. Shriver and P.W. Atkins; Oxford University Press, New York, 2004.

2.         Inorganic Chemistry, Principles of Structure and Reactivity; Fourth Edition; J.E. Huheey, E.A. Keiter and R.L. Keiter; Harper Collins 2001.

3.         Advanced Inorganic Chemistry; Sixth Edition; F.A. Cotton and G. Wilkinson; John Wiley and Sons, USA, New York, 2003.

4.         Inorganic Chemistry; Third Edition; G. L. Miessler and D. A. Tarr; Pearson Education,  New Delhi, 2007.

5.    Fundamental Concepts of Inorganic Chemistry; Volume 4 & 5, First Edition; A. K.                Das and M. Das; CBS Publishers, New Delhi, 2014.

Academic Year: 
2018-2019