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NPTEL

Introduction to Organometallic Chemistry

NPTEL and Indian Institute of Science Bangalore via YouTube

Overview

Instructor: Prof. A. G. Samuelson, Department of Inorganic and Physical Chemistry, IISc Bangalore.

This course deals with the structure, bonding and reactivity of organometallic compounds: compounds that feature a metal-carbon bond. Teaching organometallic chemistry is a daunting task for the instructor. A number of new concepts have to be introduced in the very first lecture. This happens because simple bonding models that help one understand organic compounds and metal complexes do not explain the structures and reactivity of many organometallic compounds and several new bonding models developed and refined in the last fifty years have to be suddenly thrust on the hapless student. Meanwhile, synthesis of new organometallic compounds continues unabated and has led to the study and discovery of fascinating reactions. Many of these reactions and compounds, having no similarity to what the student has been exposed to in organic chemistry giving the student no option but to memorize. So what is the best way to handle this problem? Given the diversity of “organic compounds”, and the number of “transition metals”, it is obvious that a combination of these two classes will lead to a very large “chemical space” which could be presented in various ways. One could base the chemistry of organometallic compounds on the organic ligands that are involved. Or it could be presented with a primary focus on the metal center. Sometimes, the study is centered around the reaction types. But no method is perfect. In this course an attempt is made to develop organometallic chemistry in a graded fashion, assuming only a basic understanding of organic and inorganic chemistry that one is exposed to in an undergraduate course. As much as possible, the complexity of carbon ligands attached to the metal is increased gradually. Similarly, simple reactions are dealt with first; those that do not involve a change in the oxidation state of the metal. Subsequently, more complex reactions with changes in the oxidation state are taken up  long with increase in the hapticity of the ligand. In the experience of the author interweaving structures and reactions, keeps the excitement of the student without leading to frustration and leading to excessive demands on memorization of complex reactions or structures.

Syllabus

Mod-01 Lec-01 Introduction to Organometallic chemistry.
Mod-02 Lec-02 Metal carbonyl complexes.
Mod-02 Lec-03 Metal carbonyls –Part II.
Mod-02 Lec-04 Ligand substitution reactions.
Mod-02 Lec-05 Substitutes for carbonyl ligands.
Mod-02 Lec-06 Carbene complexes.
Mod-02 Lec-07 Carbene complexes continued.
Mod-02 Lec-08 Non-Carbon Ancillary ligands.
Mod-02 Lec-09 Non-Carbon Ancillary ligands continued.
Mod-02 Lec-10 Metal alkyl complexes.
Mod-02 Lec-11 Ligand Insertion Reactions.
Mod-03 Lec-12 Metal alkene complexes.
Mod-03 Lec-13 Alkynes η2 bonding.
Mod-03 Lec-14 Metal dihydrogen and hydrides.
Mod-03 Lec-15 Migratory Insertion reaction with alkynes.
Mod-03 Lec-16 ηm (m=4 dienes and m=2n,polyenes).
Mod-04 Lec-17 Oxidative addition & Vaskas complex mechanism.
Mod-04 Lec-18 Reductive elimination.
Mod-04 Lec-19 Reductive Elimination mechanism.
Mod-04 Lec-20 Oxidative coupling with C-C bond formation.
Mod-04 Lec-21 Metathesis reactions.
Mod-05 Lec-22 Metal-allyls - η 3 complexes-synthesis, bonding.
Mod-05 Lec-23 Metal-allyls - η 3 complexes-fluxionality, reactivity.
Mod-05 Lec-24 C-C single bond forming reactions.
Mod-06 Lec-25 η 5 Cyclopentadienyl - complexes.
Mod-06 Lec-26 η6 arene Metal complexes.
Mod-06 Lec-27 Half sandwich complexes.
Mod-06 Lec-28 Reactivity changes in coordinated ligands.
Mod-07 Lec-29 The isolobal analogy.
Mod-07 Lec-30 Fluxional Properties of Organometallics.
Mod-07 Lec-31 Quantifying Steric and electronic factors.
Mod-08 Lec-32 Hydrogenation reactions.
Mod-08 Lec-33 Addition of HX to olefins.
Mod-08 Lec-34 Reactions with CO insertion.
Mod-08 Lec-35 Organometallics promoted C-X coupling.
Mod-08 Lec-36 Organometallic polymerization.
Mod-08 Lec-37 C-H activation.
Mod-09 Lec-38 Asymmetric Catalysis.
Mod-09 Lec-39 Medicinal applications of organometallic complexes.
Mod-09 Lec-40 Special Properties and Applications.

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