Inorganic Chemistry IV: Organometallic Chemistry

Paper Code: 
24CCHY611
Credits: 
4
Contact Hours: 
60.00
Max. Marks: 
100.00
Objective: 

This course will enable the students to

  • understand a basics of organometallic compounds and metal carbonyls including nomenclature, structure, bonding and the mechanism involved in homo and heterogeneous catalysis.
  • get acquainted with the kinetics and reaction mechanism of substitution reaction in octahedral and square planar complexes.

 

Course Outcomes: 

Course

Learning Outcome

(at course level)

Learning and Teaching Strategies

Assessment Strategies

Course Code

Course

title

 

24CCHY611

 

Inorganic Chemistry IV: Organometallic Chemistry

(Theory)

 

 

 

CO133: Classify and determine nomenclature of various organometallic compounds. Calculate valence electron count (18-electron) and discuss the preparation, structure and bonding of some organometallic compounds.

CO134:  Explain different methods of preparation,  properties, EAN and structure of mono and polyuclear carbonyls.

CO135: Develop a general idea of catalysis and describe the mechanism of various homogeneous and

heterogeneous organometallic catalysts.

CO136: Explain kinetics and reaction mechanism of transition metal complexes.

CO137:  Discuss S N 2 mechanism in square planar complexes and apply the concept of trans effect to identify the cis and trans isomers.

CO138: Contribute effectively in course-specific interaction.

Approach in teaching:

Interactive lectures, tutorials, group discussions and e-learning.

 

 

Learning activities for the students:

Peer learning, e-learning, problem solving through tutorials and group discussions.

 

Written examinations, assignments and quiz.

 

 

12.00
Unit I: 
Organometallic Compounds

Definition, nomenclature and classification of organometallic compounds on the basis of bond type, concept of hapticity of organic ligands, 18-electron rule, preparation, properties and structure of alkyls and aryls of Li, important structural features of methyl lithium (tetramer) and trialkyl aluminium (dimer), concept of multicentre bonding in these compounds, role of triethylaluminium in polymerisation of ethene (Ziegler – Natta catalyst), species present in ether solution of Grignard reagent and their structures, Schlenk equilibrium.

Zeise’s salt: preparation and structure, evidences of synergic effect.

Ferrocene: preparation and reactions (acetylation, alkylation, metallation, Mannichcondensation). Structure and aromaticity, comparison of aromaticity and reactivity with that of benzene.

 

12.00
Unit II: 
Metal Carbonyls

EAN rule of mononuclear, polynuclear and substituted metal carbonyls of 3d series, general methods of preparation (direct combination, reductive carbonylation, thermal and photochemical decomposition) of mono and binuclear carbonyls of 3d series, structures of mononuclear and binuclear carbonyls of Cr, Mn, Fe, Co and Ni using VBT, π-acceptor behaviour of CO (MO diagram of CO to be discussed), synergic effect and use of IR data to explain extent of back bonding and its comparison with that of Zeise’s salt.

 

12.00
Unit III: 
Catalysis by Organometallic Compounds

Principles and important reactions of transition metal organometallics: coordinative unsaturation, oxidative addition and insertion reactions.

Study of the following industrial processes and their mechanism.

Homogeneous catalysis: hydrogenation of alkenes (Wilkinson’s catalyst), hydroformylation of alkenes (co salts), Wacker process

Heterogenous catalysis: Fisher-Tropsch synthesis (synthetic gasoline), water-gas shift reaction (synthesis gas by metal carbonyl complexes).

 

12.00
Unit IV: 
Reaction Kinetics and Mechanism I

Introduction to inorganic reaction mechanisms: Energy profile of reaction transition states, patterns of reactivity and classification of mechanisms, thermodynamic and kinetic stability of metal complexes, labile and inert complexes, factors affecting the stability of complexes, kinetics of octahedral substitution, ligand field effects and reaction rates, mechanism of substitution in octahedral complexes in Co(III) complexes (acid hydrolysis).

 

12.00
Unit V: 
Reaction Kinetics and Mechanism II

Trans- effect-definition, trans effect series, theories of trans effect and uses, substitution reactions in square planar complexes of Pt (II), mechanism (SN2) of nucleophilic substitution in square planar complexes.

 

Essential Readings: 
  1. Organometallic Chemistry: A Unified Approach; Second Edition; R.C. Mehrotra and A. Singh; New Age International Private Limited, New Delhi, 2000.
  2. Inorganic Chemistry, Fifth Edition; G. L. Miessler and D. A. Tarr; Pearson Education Inc. Singapore, 2013.
  3. Principles of Inorganic Chemistry, Thirty Third Edition; B.R. Puri, L.R. Sharma, K.C. Kalia; Vishal Publishing Co., Delhi, 2020.

 

References: 
  1. Advanced Inorganic Chemistry, Sixth Edition; F.A. Cotton, G. Wilkinson, C.A. Murillo, M. Bochmann; John Wiley and Sons, USA, New York, 2007.
  2. Inorganic Chemistry (Principle and Structure and Reactivity); Fourth Edition; J. E Huheey, E. A. Keiter, R. L. Keiter; Pearson India, New Delhi, 2013.
  3. Selected Topics in Inorganic Chemistry, G.D. Tuli, R.D. Madan, W.U. Malik; S Chand and Company Ltd, New Delhi, 2019.

e-Resources:

  1. https://nptel.ac.in/courses/104101091 (Unit I)
  2. https://nptel.ac.in/courses/104108062 (Unit I)
  3. https://www.youtube.com/watch?v=Xsh3lfPgX-8 (Unit III)
  4. https://www.youtube.com/watch?v=K9BiYp8z6nA (Unit IV)
  5. https://www.digimat.in/nptel/courses/video/104101136/L46.html (Unit V)

 

Academic Year: