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Basic Organometallic Chemistry: Concepts, Syntheses and Applications
 
B D Gupta, A J Elias
Price : ₹ 725.00
ISBN : 978-81-7371-874-8
Language : English
Pages : 536
Binding : Paperback
Book Size : 180 x 240 mm
Year : 2013
Series :
Territorial Rights : WORLD
Imprint : No Image
 
 
About the Book

Organometallic chemistry is an integral part of every chemistry curriculum the world over, primarily because it bridges two main sub-disciplines of chemistry—inorganic and organic chemistry. Basic Organometallic Chemistry: Concepts, Syntheses and Applications, Second Edition

  • covers a large variety of topics in detail;
  • includes several new topics supplemented with relevant figures;
  • is lavishly complemented with figures, equations and schemes for easy comprehension;
  • includes carefully selected, updated and comprehensive references;
  • provides a number of problems and exercises to test understanding;
  • provides detailed solutions to the problems as appendices;
is useful for M.Sc chemistry students and researchers in many areas of chemistry.
Table of Contents

Chapter 1 Introduction
1.1 What is organometallic chemistry?
1.2 A brief history of organometallic chemistry
1.3 Importance of organometallic compounds
1.3.1 Organometallic compounds as reagents
1.3.2 Organometallic compounds as additives
1.3.3 Organometallic compounds as catalysts
Supplementary reading
Chapter 2 The 18 Valence Electron Rule
2.1 Introduction
2.2 The 18 electron rule
2.3 Counting of electrons and finding metal–metal bonds
2.4 Compliance and violation of the 18 electron rule
Problems and exercises
Supplementary reading
Chapter 3 Metal Carbonyls
3.1 Structure, p-bonding and infrared spectroscopy
3.2 Bonding modes of CO
3.3 Symmetry of metal carbonyls
3.4 Syntheses of metal carbonyls
3.4.1 Direct carbonylation
3.4.2 Reductive carbonylation
3.5 Reactions of metal carbonyls
3.5.1 Activation of metal carbonyls
3.5.2 Disproportionation
3.5.3 Nucleophilic addition to CO
3.5.4 Electrophilic addition to the carbonyl oxygen
3.5.5 Carbonyl anions, cations and hydrides
3.5.6 Collman’s reagent
3.5.7 Migratory insertion of carbonyls
3.5.8 Oxidative decarbonylation
3.5.9 Photochemical substitution
3.5.10 Microwave assisted substitution
3.6 Metal nitrosyls
Problems and exercises
Supplementary reading
Chapter 4 Neutral Spectator Ligands: Phosphines and N-heterocyclic Carbenes
4.1 Phosphines: steric and electronic parameters
4.2 Basicity of phosphines
4.3 Monodentate phosphines
4.4 Multidentate phosphines
4.5 N-Heterocyclic carbenes
4.5.1 Synthesis of NHCs
Problems and exercises
Supplementary reading
Chapter 5 Alkenes and Alkynes as Ligands
5.1 Models of ethylene–metal bonding
5.2 Synthesis of metal-alkene complexes
5.3 Reactions of metal bound alkenes: The concept of Umpolung
5.4 Alkynes: modes of bonding to metals
5.5 Reactions of metal complexes of alkenes and alkynes
5.5.1 Pauson–Khand reaction
Problems and exercises
Supplementary reading
Chapter 6 Carbenes and Carbynes: Complexes with Metal–Carbon Double and Triple Bonds
6.1 Metal carbenes
6.1.1 Synthesis of Fischer carbene complexes
6.1.2 Synthesis of Schrock carbene complexes
6.1.3 Tebbe’s reagent
6.1.4 Carbenes that are intermediate between the Fischer and Schrock types
6.2 Metal carbynes
6.2.1 Synthesis of metal–carbyne complexes
6.2.2 Reactions of metal–carbyne complexes
Problems and exercises
Supplementary reading
Chapter 7 Alkyl, Aryl and Ligands with Higher Hapticity
7.1 s bonded alkyl groups as ligands
7.1.1 Synthesis of metal–alkyl compounds
7.1.2 ß-Hydride elimination
7.1.3 s bonded ?1-aryl ligands
7.2 Cyclic and acyclic polyenyl p bonded ligands
7.2.1 Cyclopentadienyl (Cp–)
7.2.2 Synthesis of Cp based sandwich compounds
7.2.3 Structure and properties of MCp2 complexes
7.2.4 Ferrocene: The first metal-sandwich compound
7.2.5 Reactions of metal-sandwich compounds
7.2.6 Bent sandwich compounds
7.2.7 Schwartz’s reagent and hydrozirconation
7.2.8 Chemistry of Cp*
7.2.9 Chemistry of arene sandwich compounds
7.2.10 Allyl groups as ligands
7.2.11 1,3-Butadiene complexes
7.2.12 Cyclobutadiene complexes
7.2.13 Cycloheptatriene and cyclooctatetraene as ligands
7.3 Davies–Green–Mingos (DGM) rules
Problems and exercises
Supplementary reading
Chapter 8 Unique Reactions in Organometallic Chemistry
8.1 Oxidative addition and oxidative coupling
8.1.1 Oxidative addition involving C–X bonds
8.1.2 Prelude to cyclometallation: Agostic and anagostic interactions
8.1.3 Oxidative addition involving C–H bonds and cyclometallation
8.1.4 Orthometallation
8.1.5 Oxidative addition involving C–C bonds
8.1.6 Oxidative addition of ligands with p systems (Oxidative coupling)
8.2 Reductive elimination
8.2.1 Mononuclear systems
8.2.2 Binuclear systems
8.3 Migratory insertion reactions
8.3.1 Lewis acid acceleration
8.3.2 Redox acceleration
8.3.3 Migration versus insertion
8.3.4 Insertion of alkenes
8.3.5 ß-Hydrogen elimination versus reductive elimination
Problems and exercises
Supplementary reading
Chapter 9 Ligand Substitution Reactions and Fluxionality in Organometallic
Compounds
9.1 Types of ligand substitution reactions
9.1.1 Activation entropy and activation volume
9.1.2 Factors affecting substitution reactions
9.2 Associative substitutions
9.2.1 Hapticity change in mulitdentate ligands
9.3 Dissociative substitutions
9.4 Interchange mechanisms
9.4.1 Associative interchange
9.4.2 Dissociative interchange
9.5 Stereochemical non-rigidity in organometallic compounds
9.5.1 Ring whizzing in ?1-Cp complexes
9.5.2 Interchange of ?1- and ?5-Cp rings
9.5.3 Allyl complexes
9.5.4 Allene complexes
9.5.5 Scrambling of carbonyl groups in metal carbonyls
Problems and exercises
Supplementary reading
Chapter 10 Metal Clusters
10.1 Introduction
10.2 Dinuclear clusters
10.2.1 A five fold bonded organometallic compound
10.3 Multinuclear carbonyl clusters
10.3.1 Low nuclearity carbonyl clusters
10.3.2 High nuclearity carbonyl clusters (HNCC)
10.3.3 Electron counting schemes for high nuclearity clusters
10.3.4 Capping rules
10.3.5 Limitations and exceptions
10.3.6 Polyhedral skeletal electron pair approach or Mingo’s rules
10.3.7 Carbide clusters
10.4 The isolobal analogy
10.4.1 Clusters having interstitial main group elements
10.5 Synthesis of metal carbonyl clusters
10.6 Reactions of metal carbonyl clusters
Problems and exercises
Supplementary reading
Chapter 11 Homogeneous Catalysis Using Organometallic Compounds
11.1 Catalysis
11.2 Terminology in catalysis
11.2.1 Turnover
11.2.2 Turnover number (TON)
11.2.3 Turnover frequency (TOF) or turnover rate
11.3 Sequences involved in a catalysed reaction
11.4 Other important terminology used in catalysis
11.5 Asymmetric synthesis using a catalyst
11.6 Heterogeneous catalysis
11.6.1 Catalytic converters in automobiles
11.7 Feedstock for the chemical industry
Problems and exercises
Supplementary reading
Chapter 12 Catalytic Hydrogenation of Alkenes and Related Reactions
12.1 Hydrogenation catalysts
12.1.1 Classification of hydrogenation catalysts
12.1.2 Catalytic cycle of Wilkinson’s catalyst
12.1.3 Catalytic cycles of iridium and ruthenium based catalysts
12.1.4 Directing effects in catalytic hydrogenation
12.1.5 Hydrogenation by lanthanide organometallic compounds
12.2 Catalytic asymmetric synthesis
12.2.1 The first industrial catalytic asymmetric hydrogenation
12.2.2 The mechanism of asymmetric hydrogenation using a chiral catalyst
12.2.3 Asymmetric hydrogenation of ketones and isomerisation
12.2.4 Asymmetric hydrogen transfer
12.3 Hydrocyanation of alkenes
12.4 Hydrosilylation of alkenes
Problems and exercises
Supplementary reading
Chapter 13 Hydroformylation
13.1 Importance of hydroformylation
13.2 Cobalt catalysts for hydroformylation
13.3 Phosphine modified cobalt catalysts
13.4 Rhodium–phosphine catalysts
13.5 Factors affecting the n/iso ratio of hydroformylation products
13.6 Enantioselective hydroformylation
13.7 Carboalkoxylation of olefins
Problems and exercises
Supplementary reading
Chapter 14 Methanol Carbonylation and Olefin Oxidation: Monsanto, Cativa and Wacker
Processes
14.1 History of methanol carbonylation
14.2 The Monsanto process
14.2.1 Problems with the Monsanto process
14.3 Celanese process using LiI modified rhodium catalyst
14.4 Tennessee Eastman acetic anhydride process
14.5 British Petroleum’s Cativa process
14.6 The Wacker process
Problems and exercises
Supplementary reading
Chapter 15 Olefin Metathesis
15.1 Olefin metathesis as a synthetic tool
15.2 Well known olefin metathesis catalysts and their properties
15.3 Synthesis of Grubbs’ and Schrock catalysts
15.4 Mechanism of olefin metathesis
15.4.1 Ring opening metathesis (ROM)
15.4.2 Cross metathesis (CM)
15.4.3 Ring closing metathesis (RCM)
15.4.4 Ring opening metathesis polymerisation (ROMP)
15.4.5 Acyclic diene metathesis polymerisation (ADMET)
15.4.6 Enyne metathesis (EM)
15.5 Comparison of catalysts
15.6 Metathesis of hindered olefins
15.7 Applications of catalytic olefin metathesis
15.8 Alkyne metathesis
Problems and exercises
Supplementary reading
Chapter 16 Palladium Catalysed C–C and C–N Cross Coupling Reactions
16.1 Discovery of palladium based cross coupling reactions
16.2 Industrial applications of cross coupling reactions
16.3 The cross coupling catalyst
16.4 The Heck reaction
16.5 Suzuki–Miyaura coupling
16.6 Sonogashira coupling
16.7 Stille coupling
16.8 Kumada coupling
16.9 Negishi coupling
16.10 Hiyama coupling
16.11 Buchwald–Hartwig C–N cross coupling
16.12 Cross coupling reactions in aqueous media with functional group tolerance
16.13 Cross coupling reactions of organohalides with non-organometallic and non-heteroatom based
reagents
Problems and exercises
Supplementary reading
Chapter 17 Olefin Polymerisation and Oligomerisation Reactions
17.1 Catalysts for olefin polymerisation
17.2 Types of polyethylene and polypropylene
17.2.1 Polyethylene
17.2.2 Polypropylene
17.3 The Ziegler–Natta catalyst
17.4 Site control and chain end control mechanisms
17.5 Metallocene based catalysts
17.5.1 Polypropylenes using metallocenes
17.5.2 The mechanism of propylene polymerisation by metallocenes
17.5.3 Polypropylene and stereochemistry
17.5.4 Stereo-block polypropylene
17.5.5 Constrained geometry catalysts
17.6 Post-metallocene catalysts
17.6.1 The Brookhart catalysts
17.6.2 Fenokishi Imin (FI) and related ligand based metal catalysts
17.7 Olefin oligomerisation reactions
17.7.1 Shell’s higher olefin process
Problems and exercises
Supplementary reading
Chapter 18 Ferrocene: Structure, Bonding and Reactions
18.1 Structure and bonding of ferrocene
18.2 The reactions of ferrocene and its derivatives
18.2.1 Basic chemical reactions of ferrocene
18.2.2 Reactions of acetyl ferrocene and formyl ferrocene
18.2.3 Lithiated ferrocenes and their reactions
18.2.4 (Dimethylaminomethyl)ferrocene and its methiodide salt
18.2.5 Ferrocene boronic acid and haloferrocenes
18.3 Ferrocene derivatives in asymmetric catalysis
18.3.1 Chirality in ferrocene derivatives
18.3.2 Synthesis of chiral ferrocene based compounds
Problems and exercises
Supplementary reading
Chapter 19 Organometallic Polymers
19.1 Polymers with organometallic moieties as pendant groups
19.2 Polymers with organometallic moieties in the main chain
19.2.1 Ferrocene based condensation polymers
19.2.2 Condensation polymers based on rigid rod polyynes
19.2.3 Polymers prepared by ring opening polymerisation process
19.3 Organometallic dendrimers
19.3.1 Synthesis of dendrimers: Divergent and convergent methods
Problems and exercises
Supplementary reading
Chapter 20 Bioorganometallic Chemistry
20.1 Introduction
20.2 Organometallic enzymes and coenzymes
20.2.1 Vitamin B12 coenzyme: ‘Nature’s most beautiful cofactor’
20.2.2 Nomenclature and structure
20.2.3 Correnoid dependant enzymatic reactions
20.2.4 Vitamin B12 model compounds
20.3 Role of organometallics in heavy metal poisoning
20.3.1 Heavy metal toxicity: Mercury related cases
20.3.2 Arsenic poisoning
20.4 Organometallic compounds as drugs
20.4.1 ?6-Aryl–ruthenium compounds as general anticancer drugs
20.4.2 Ferroquine as antimalarial drug
20.4.3 Ferrocifen as breast cancer drug
20.5 Organometallics as radiopharmaceuticals, tracers, ionophores and sensors
20.5.1 Radiopharmaceuticals
20.5.2 Organometallic tracers
20.5.3 Organometallics as ionophores
20.5.4 Organometallic compounds as sensors
Problems and exercises
Supplementary reading
Appendix 1: Solutions to problems and exercises
Appendix 2: Quick revision questions

Contributors (Author(s), Editor(s), Translator(s), Illustrator(s) etc.)

B D Gupta (Late) was professor, Department of chemistry, IIT Kanpur. After completing his Ph D from Flinders University, Australia, he worked as a post-doctoral researcher at the University College, London. After a one-year teaching stint at Roorkee University (now IIT Roorkee), he joined IIT Kanpur where he taught undergraduate, graduate and postgraduate students for over 30 years. He taught undergraduate classes for many years at various universities in the USA and Japan. He has published more than 90 research papers in international journals of repute in the area of organometallic chemistry of cobalt compounds.

Anil J Elias is professor, Department of chemistry, IIT Delhi. After completing his Ph D in inorganic chemistry from IIT Madras, he gained further experience as an Alexander von Humboldt fellow in Germany and later at the Fluorine Research Laboratories of the University of Idaho, USA. He has been teaching undergraduate, graduate and postgraduate students at IIT Kanpur and IIT Delhi for over 20 years. His research interests are in the area of organometallic and main group chemistry. He has authored the book General Chemistry Experiments: An interesting Collection (Universities Press) and published more than 55 research papers in reputed international journals. Prof. Elias is the recipient of the INSA teacher’s award instituted by the Indian National Science Academy for excellence in teaching science.

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