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Introduction to Organometallic Chemistry: This course deals with 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 continue unabated and have 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 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 centre. 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 along 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.

Module No.

Topics

1.

INTRODUCTION

 

1.Introduction To Organometallic Chemistry

2.

C1 LIGANDS AND SIMPLE REACTIONS

 

02. Metal carbonyl complexes
03. Metal carbonyls –Part II
04. Ligand substitution reactions
05. Substitutes for carbonyl ligands
06. Carbene complexes
07. Carbene complexes continued
08. Non-Carbon Ancillary ligands  
09. Non-Carbon Ancillary ligands continued
10. Metal alkyl complexes
11. Ligand Insertion Reactions

3.

ηm  (m=even) ligands

 

12. Metal alkene complexes
13. Alkynes η2 bonding
14. Metal dihydrogen and hydrides
15. Migratory Insertion reaction with alkynes
16.ηm  (m=4 dienes and m=2n, polyenes)

4.

Reactions with oxidation state change

 

17. Oxidative addition & Vaskas complex mechanism
18. Reductive elimination
19. Reductive Elimination mechanism
20. Oxidative coupling with C-C bond formation
21. Metathesis reactions

5.

ηm  (m=odd)  ligands

 

22. Metal-allyls - η3 complexes-synthesis, bonding
23. Metal-allyls - η3 complexes-fluxionality, reactivity
24. C-C single bond forming reactions

6.

Metallocenes

 

25. η5 Cyclopentadienyl - complexes
26. η6  arene  Metal complexes
27. Half sandwich complexes
28. Reactivity changes in coordinated ligands

7.

Dynamics and structures of organometallic compounds

 

29. The isolobal analogy
30. Fluxional Properties of Organometallics
31. Quantifying Steric and electronic factors

8.

Useful catalytic and Stoichiometric reactions

 

32. Hydrogenation reactions
33. Addition of HX to olefins
34. Reactions with CO insertion
35. Organometallics promoted C-X coupling
36. Organometallic polymerization
37. C-H activation

9.

Applications of organometallic chemistry

 

38. Asymmetric Catalysis
39. Medicinal applications of organometallic complexes
40. Special Properties and Applications

Basic Inorganic and Organic Chemistry


Title:Organometallics:A Concise Introduction

Authors:Christoph Elschenbroich

Year:2006

Publisher:Wiley-VCH3rd Edition

ISBN-13:978-3-527-29390-2

Title:Basic Organometallic Chemistry:Concepts, Syntheses and Application

Authors:BD Gupta & Anil J Elias Year:2013

Publisher:Universities Press

ISBN:978-81-7371-709-3


Title:Fundamentals of Organometallic Catalysis

Author:Dirk Steinborn

Year:2012

Publisher:Wiley-VCH

ISBN:978-3-527-32717-1


Title:Organometallic Chemistry and Catalysis

Author:Didier Astruc

Year:2007

Publisher:Springer

ISBN:978-3-540-46129-6


The Organometallic HyperTextBook Index


COMPREHENSIVE ORGANOMETALLIC CHEMISTRY II, 14-VOLUME SET, by E.W. Abel, University of Exeter, UK G. Wilkinson, Imperial College of Science, Technology & Medicine, UK F.G.A. Stone, Baylor University, USA Elsevier



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