Organometallic Chemistry

Teacher

Dr. Arun Kumar Pradhan

Category

Core Courses

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Course Name :Organometallic Chemistry

Code (Credit):CUTM1481(3-2-1)

Course Objectives

  • The main focus of this course is on the synthesis, structure, bonding, properties and reactivity of organometallic compounds such as: metal carbonyls, hydrocarbon, and carbocyclic based molecules.

  •  This course also covers, 18-electron rule (Saturation and Unsaturation), Organometallic reaction (substitution, oxidative-addition, reductive elimination, insertion and de-insertion, and  isomerization).

Learning Outcomes

  • By the completion of the course, students will get a good overview of the fundamental principles of organotransition-metal chemistry.

  • Have insight into the use of modern methods to characterize organometallic compounds.

  • Students will understand fundamental reaction types and mechanisms and how to combine these to understand efficient catalytic processes, know important applications of organometallic homogeneous catalysis in the production of large-scale (bulk) and smaller-scale (fine chemicals) production.

Course Syllabus

Module I (8 hours)
Organometallic Compounds Definition and classification of organometallic compounds
The different organometallic Compounds the basis of bond type.Concept of hapticity of organic ligands.

Assignment -1/Flip-class-1 : Concept of hapticity of organic ligands

Practice -1 : Estimation of Fe(II) with K2Cr2O7

Practice -2:  Qualitative Analysis

Module II (12 hours)
Metal carbonyls: 18 electron rule electron count 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.Organ metallic Compounds with metal-metal bond Cluster.Structures of mononuclear and binuclear carbonyls of Cr, Mn, Fe, Co and Ni using VBT.Pi-acceptor behaviour of CO (MO diagram of CO to be discussed.

Assignment -2/Flip-class-2 : Pi-acceptor behaviour of CO (MO diagram of CO to be discussed)

Practice -3 : Identifying  anions

Practice -4: Identifying  anions

Module III ( 9 hours)
Synergic effect organometallic compounds having ligands with back bonding as metal carbonyl. metal carbenes, metal nitrosyls, IR data to explain extent of back bonding.

Assignment -3/Flip-class-3 : IR data to explain extent of back bonding

Practice -5 :Identifying  anions

Practice -6:Identifying  anions

Module IV ( 11 hours)
Zeise’s salt: Preparation and structure, evidences of synergic effect and comparison of synergic effect with that in carbonyls.
Metal Alkyls: Important structural features of methyl lithium (tetramer) and trialkylaluminium (dimer), concept of multicentre bonding in these compounds.
Role of triethylaluminium in polymerisation of ethene (Ziegler - Natta Catalyst).
Ferrocene: Preparation and reactions (acetylation, alkylation, metallation, Mannich Condensation). Structure and aromaticity.Comparison of aromaticity and reactivity with that of benzene.

Assignment -4/Flip-class-4 : Concept of multicentre bonding in these compounds.

Assignment -5/Flip-class-5 :Structure and aromaticity.Comparison of aromaticity and reactivity with that of benzene.

Assignment -6/Flip-class-6 :  Preparation and reactions (acetylation, alkylation, metallation, Mannich Condensation).

Practice -7 : Identifying  cations

Practice -8: Identifying  cations

Practice -9 : Identifying  cations

Practice -10: Identifying  cations

Module V (5 hours)
Reaction Kinetics and Mechanism Introduction to inorganic reaction mechanisms.
Substitution reactions in square planar complexes,
Transeffect, theories of trans effect,
Mechanism of nucleophilic substitution in square planar complexes.

Module VI (6 hours)

Thermodynamic and Kinetic stability,
Kinetics of octahedral substitution ,Ligand field effects and reaction rates,
Mechanism of substitution in octahedral complexes.Catalysis by Organometallic Compounds

Assignment -7/Flip-class-7 : Mechanism of substitution in octahedral complexes.Catalysis by Organometallic Compounds

Assignment -8/Flip-class-8 : Kinetics of octahedral substitution ,Ligand field effects and reaction rates

Practice -1 1:Identifying  cations

Module VII (8 hours)
Study of the following industrial processes and their mechanism: 1. Alkene hydrogenation (Wilkinsons Catalyst)
Hydroformylation (Co salts)
Wacker Process
Synthetic gasoline (Fischer Tropsch reaction)

Assignment -9/Flip-class-9:Study of the following industrial processes and their mechanism: 1. Alkene hydrogenation (Wilkinsons Catalyst),Hydroformylation (Co salts)

Assignment -10/Flip-class-10: Synthetic gasoline (Fischer Tropsch reaction) ,Wacker Process.

Practice -1 2:

Identifying  cations

BOOKS RECOMMENDED

1.Inorganic Chemistry ; Ajay kumar

2.Inorganic Chemistry By Madan Malik Tuli

3.principal of inoganic chemistry by puri sharma kalia

Reference Books:

1.Huheey, J. E.; Keiter, E.A. & Keiter, R.L. Inorganic Chemistry, Principles of Structure and Reactivity 4th Ed., Harper Collins 1993, Pearson,2006.

2.Sharpe, A.G. Inorganic Chemistry, 4th Indian Reprint (Pearson Education) 2005

3.Douglas, B. E.; McDaniel, D.H. & Alexander, J.J. Concepts and Models in Inorganic Chemistry3rd Ed., John Wiley and Sons, NY, 1994.

4.Greenwood, N.N. & Earnshaw, A. Chemistry of the Elements, Elsevier 2nd Ed, 1997 (Ziegler Natta Catalyst and Equilibria in Grignard Solution).

5.Lee, J.D. Concise Inorganic Chemistry 5th Ed., John Wiley and sons 2008.

6.Powell, P. Principles of Organometallic Chemistry, Chapman and Hall, 1988

Session Plan

Session 1 (1 -hour)

Organometallic Compounds Definition and classification of organometallic compounds
https://www.youtube.com/watch?v=ITfwjQemwMg

References

https://www.youtube.com/watch?v=aK-nCRPMQUo

https://www.youtube.com/watch?v=w3tuNuJ3cyA&t=487s

https://www.youtube.com/watch?v=8pqCeN7GoMc&list=PLj_Alq7xw30kcuwE26FhkG5YD23zL4cEL

Session 2 (1- hour )

The different organometallic Compounds the basis of bond type.

https://uomustansiriyah.edu.iq/media/lectures/6/6_2017_03_14!12_38_50_AM.pdf

Session 3 (1- hour )

Session 4 (1-hour-Assignment -1/Flip-class-1)

Concept of hapticity of organic ligands

Session 5 (2-hour-Practice -1)

Session 6 (2-hours-Practice -2)

Session 7(1-hour)

Session 8(1-hour )

Metal carbonyls: 18 electron rule electron count of mononuclear, polynuclear and substituted metal carbonyls of 3d series
https://www.youtube.com/watch?v=sSS5QKo7yyI

https://www.youtube.com/watch?v=LE-TpS3knoQ

Session 9 (1 -hour )

General methods of preparation (direct combination, reductive carbonylation

https://www.youtube.com/watch?v=PnMc6PN82mc

Session 10 (1-hour )

Thermal and photochemical decomposition) of mono and binuclear carbonyls of 3d series
https://www.youtube.com/watch?v=PnMc6PN82mc

Session 11 (1- hour )

Organ metallic Compounds with metal-metal bond Cluster

https://www.youtube.com/watch?v=mhZxYkJlFEU

Reference

https://www.youtube.com/watch?v=1xbBYBZDv3s

Session 12(1- hour )

Structures of mononuclear and binuclear carbonyls of Cr, Mn, Fe, Co and Ni using VBT
https://www.youtube.com/watch?v=86rNPVAtj0Y

Session 13(1- hour )

Pi-acceptor behaviour of CO (MO diagram of CO to be discussed)
https://www.youtube.com/watch?v=PnMc6PN82mc
https://www.youtube.com/watch?v=darVtuigUJA

Session 14(1-hour-Assignment-2/Flip-class-2)

Pi-acceptor behaviour of CO (MO diagram of CO to be discussed)

https://www.youtube.com/watch?v=RFxZ9YnltZ8

Session 15 (2-hours-Practice -3)

Session 16 (2-hours-Practice -4)

Session 17(1 -hour )

Session 18 (1- hour )

Session 19 (1- hour )

Session 20(1- hour)

IR data to explain extent of back bonding
https://www.youtube.com/watch?v=8qbuZ89JW_o

Session 21( 1-hour-Assignment-3 /Flip-class-3)

IR data to explain extent of back bonding

Session 22(2-hour-Practice -5) 

Session 23(2-hours-Practice -6) 

Session 24 (1 -hour )

Metal Alkyls: Important structural features of methyl lithium (tetramer) and trialkylaluminium (dimer)
https://www.youtube.com/watch?v=OyxFKDWsypE

Session 25 (1- hour )

Concept of multicentre bonding in these compounds.
https://www.youtube.com/watch?v=OyxFKDWsypE

Session 26 ( 1-hour-Assignment-4/Flip-class-4)

Concept of multicentre bonding in these compounds

Cations (Zn(II), Al(III), Cu(II), Fe(II) and Fe(III): Tested with NaOH

https://www.youtube.com/watch?v=3COr0ol1AxM

Session 28(2-hours-Practice -8) 

Session 29(1- hour )

Zeise’s salt: Preparation and structure, evidences of synergic effect
https://www.youtube.com/watch?v=AS8qvQCjpww

Session30 (1- hour )

comparison of synergic effect with that in carbonyls.
https://www.youtube.com/watch?v=AS8qvQCjpww

Session 31 (1 hour )

Role of triethylaluminium in polymerisation of ethene (Ziegler - Natta Catalyst).
https://www.youtube.com/watch?v=UB3wiRNFlK0

Session 32(1- hour)

Ferrocene: Preparation and reactions (acetylation, alkylation, metallation, Mannich Condensation).
https://www.youtube.com/watch?v=HvwswG8FmqE

Session 33(1 -hour)

Structure and aromaticity.Comparison of aromaticity and reactivity with that of benzene.
https://www.youtube.com/watch?v=HvwswG8FmqE

Session 34( 1-hour-Assignment-5/Flip-class-5)

Structure and aromaticity.Comparison of aromaticity and reactivity with that of benzene.

Session 35(1-hour-Assignment-6/Flip-class-6)

Ferrocene: Preparation and reactions (acetylation, alkylation, metallation, Mannich Condensation)

Session 36(2-hours-Practice -9) 

 Identefay  cations

https://www.youtube.com/watch?v=3sOCGx5NC2o&t=958s

Reference

https://www.youtube.com/watch?v=bKmLUhihohQ&t=251s

Session 38(1 -hour )

Reaction Kinetics and Mechanism Introduction to inorganic reaction mechanisms
https://www.youtube.com/watch?v=n4cIKKI3_eU
http://epgp.inflibnet.ac.in/epgpdata/uploads/epgp_content/S000005CH/P000658/M019072/ET/1515586647CHE_P3_M22_etext.pdf

https://www.youtube.com/watch?v=AjPug12EgH0

Session 39(1- hour)

Substitution reactions in square planar complexes
https://www.youtube.com/watch?v=yBPoLId6EjA

Session 40 (1- hour)

Session41 (1- hour)

Mechanism of nucleophilic substitution in square planar complexes
https://www.youtube.com/watch?v=yBPoLId6EjA

Session 42 (1-hour)

Session 43 (1- hour)

Session 44 (1- hour)

Session 45 (1 -hour-Assignment-7/Flip-class-7)

Mechanism of substitution in octahedral complexes.Catalysis by Organometallic Compounds

Session 46 (1 -hour-Assignment-8/Flip-class-8)

Kinetics of octahedral substitution ,Ligand field effects and reaction rates

Session 47(2-hours-Practice -11) 

 Identefay  cations

Session 48 (1-hour)

Study of the following industrial processes and their mechanism: 1. Alkene hydrogenation (Wilkinsons Catalyst)
Hydroformylation (Co salts)

https://www.youtube.com/watch?v=04XP1WlGcuE
https://www.youtube.com/watch?v=04XP1WlGcuE

https://www.youtube.com/watch?v=vnVMS_Dp0dU http://sas.k.u-tokyo.ac.jp/AZ/Lecture10.pdf

Session 49 (1- hour)

Session 50 (2- hours-Assignment-9/Flip-class-9)

Study of the following industrial processes and their mechanism: 1. Alkene hydrogenation (Wilkinsons Catalyst)
Hydroformylation (Co salts)

Session 51(2 -hours- Assignment-10/Flip-class-10)

Synthetic gasoline (Fischer Tropsch reaction)

Wacker Process

Session 52(2-hour-Practice -12) 

Identifying  cations

Our Main Teachers

Dr. Arun Kumar Pradhan completed his M.Sc. degree in 2010, M.Phil. degree in 2011, and Ph.D. in 2017 from Utkal University. After completed his M.Phil. degree he joined F.M. Autonomous College, Balasore as a guest faculty. At the same time,  he qualified CSIR-JRF with all India rank 72, in General Chemistry in 2012. After that, […]