Organometallic Compounds E-Book
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Organometallic Compounds
An up-to-date overview of the fundamentals, synthesis, and applications of organometallic compounds
Organometallic Compounds: Synthesis, Reactions, and Applications delivers an accessible and robust introduction to the fundamentals of organometallic compounds, including their reactions, catalytic mechanisms, and modern applications, including carbon-dioxide fixation, reduction, gas adsorption and purification, drug delivery, renewable energy, and wastewater treatment. The book also covers toxicological and computational studies.
The authors address the current challenges confronting researchers seeking to sustainably synthesize and process organometallic compounds and offer complete coverage on the most recent advancements in applications relating to the fields of environmental science, electronics, fossil fuels, and more.
Readers will also find:
- Introduces to fundamentals, nomenclature, properties, and classification of organometallic compounds
- Discusses methods of synthesis of organometallic compounds
- Practical discussions of organometallic complexes of the lanthanoids and actinoids, as well as bio-organometallic chemistry
- Includes characterization techniques of organometallic compounds
Perfect for organic, environmental, inorganic, water, and catalytic chemists, Organometallic Compounds: Synthesis, Reactions, and Applications will also benefit chemical engineers and industrial chemists.
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Seitenzahl: 598
Veröffentlichungsjahr: 2023
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Table of Contents
Cover
Title Page
Copyright
Preface
About the Editors
1 Organometallic Compounds: The Fundamental Aspects
1.1 Introduction
1.2 Milestones in Organometallic Compounds
1.3 Stability of Organometallic Compounds
1.4 Properties of Organometallic Compounds
1.5 Basic Concepts in Organometallic Compounds
1.6 Hapticity of Ligands
1.7 Change in Hapticity
1.8 Hapticity Verses Denticity
1.9 Counting of Electrons and Finding out Metal–Metal Bonds
1.10 Metals of Organometallic Compounds
1.11 Importance of Organometallic Compounds
1.12 Conclusions
References
2 Nomenclature of Organometallic Compounds
2.1 Introduction
2.2 Aim of the Nomenclature
2.3 Type of Nomenclature System
2.4 Concepts and Conventions
2.5 Regulations Concerning the Nomenclature of Transition Element Organometallic Compounds
References
3 Classification of Organometallic Compounds
3.1 Introduction
3.2 Classification of Organometallic Compound
3.3 Grignard Reagent (G.R.)
3.4 Organozinc Compounds
3.5 Organolithium Compounds
3.6 Organosulfur Compounds
3.7 Conclusion
References
4 Synthesis Methods of Organometallic Compounds
4.1 Introduction
4.2 Synthesis Methods of Organometallic Compounds
4.3 Conclusions
Acknowledgment
Authors Contributions
Conflicts of Interest
References
5 Metal Carbonyls: Synthesis, Properties, and Structure
5.1 Introduction
5.2 Classification of Metal Carbonyls [4]
5.3 Synthesis of Metal Carbonyls
5.4 Properties of Metal Carbonyls
5.5 Structure of Metal Carbonyls
5.6 Bonding in Metal Carbonyls
5.7 Synergistic Effect
5.8 Conclusion
Further Reading
References
6 Metal–Carbon Multiple Bonded Compounds
6.1 Introduction
6.2 Nomenclature
6.3 Classifications
6.4 Structure
6.5 Preparation Methods
6.6 Important Reactions
6.7 Applications
References
7 Metallocene: Synthesis, Properties, and Structure
7.1 Introduction
7.2 Structure of Metallocene
7.3 Synthesis of Metallocene
7.4 Chemical Properties of Metallocene
7.5 Conclusion
References
8 σ‐Complexes, π‐Complexes, and η
n
‐C
n
R
n
Carbocyclic Polyenes‐Based Organometallic Compounds
8.1 Introduction
8.2 σ‐Bond Containing Organometallic Compounds
8.3 π‐Bond Containing Organometallic Compounds
8.4 η
n
‐C
n
R
n
Carbocyclic Polyenes Containing Organometallic Compounds
8.5 Conclusion
References
9 Organometallic Complexes of the Lanthanides and Actinides
9.1 Introduction
9.2 Methods of Preparation
9.3 Organometallic Compounds of Lanthanides
9.4 Organometallic Compounds of Actinides
9.5 Stability
9.6 Properties
9.7 Applications of Organolanthanoids and Organoactinoids
9.8 Conclusion
Further Reading
Note
10 Bioorganometallic Chemistry
10.1 Introduction
10.2 Cobalamin: Vitamin B
12
‐Coenzyme
10.3 Metalloproteins
10.4 Oxidoreductase
Cytochrome P‐450
10.5 Nitrogenases‐catalyzing Nitrogen Fixation
10.6 Nickel Enzymes: CODH
10.7 Conclusion
References
11 Important Reactions of Organometallic Compounds
11.1 Introduction
11.2 Reactions Involving Gain or Loss of Ligands
11.3 Reductive Elimination and Pd‐catalyzed Cross Coupling
11.4 Reactions Involving Modification of Ligands
11.5 Conclusion
References
Note
12 Characterization Techniques of Organometallic Compounds
12.1 Introduction
12.2 Conventional Methods
12.3 Unconventional Methods
12.4 Conclusion
References
13 Organometallic Reagents
13.1 Organoboron Reagents
13.2 Organocopper Reagents
13.3 Organopalladium Reagents
13.4 Grignard Reagents
References
14 Homogeneous and Heterogeneous Catalysis by Organometallic Complexes
14.1 Introduction
14.2 Organometallic Compounds and Homogeneous Catalysis
14.3 Catalytic Elementary Reactions
14.4 Hydrogenation
14.5 Carbon–Carbon Bond Formation
14.6 Metathesis
14.7 Oxidation
14.8 Reactions with Carbon Monoxide
14.9 Heterogenous Catalysis
14.10 Conclusion
References
Note
15 Cluster Compounds: Boranes, Heteroboranes, and Metallaboranes
15.1 Introduction
15.2 Main Part
15.3 Conclusion
References
16 Applications of Organometallic Compounds for Carbon Dioxide Fixation, Reduction, Gas Adsorption, and Gas Purification
16.1 Organometallic Compounds for Fixation of CO
2
16.2 Organometallic Compounds in Reduction of CO
2
16.3 Organometallic Compounds in Gas Adsorption and Purification
16.4 Gas Purification with MOFs
References
17 Emerging Role of Organometallic Compounds for Drug Delivery, Renewable Energy, and Wastewater Treatment
17.1 Introduction
17.2 Organometallic Compounds
17.3 Organometallic Compounds for Drug Delivery
17.4 Organometallic Compounds for Renewable Energy
17.5 Organometallic Compounds for Wastewater Treatment
17.6 Conclusion
17.7 Outlook
Acknowledgment
References
18 Computational Approaches in Some Important Organometallic Catalysis Reaction
18.1 Introduction
18.2 Computational Method
18.3 Organometallic Catalysis Reactions
18.4 Conclusion
References
Index
End User License Agreement
List of Tables
Chapter 1
Table 1.1 Differences between hapticity verses denticity[40].
Chapter 2
Table 2.1 Few examples of negatively charged ligands.
Table 2.2 Few examples of neutral ligands.
Table 2.3 Few common organic ligands and their names.
Table 2.4 Organic ligand their systematic substitutive and systematic additi...
Table 2.5 Ligands that coordinate during the formation of metal–carbon multi...
Table 2.6 Names of organic ligands with unsaturated groups and molecules.
Table 2.7 Prefixes for complex and simple ligands.
Chapter 3
Table 3.1 Electron donation by unsaturated compound various heptacity.
Chapter 5
Table 5.1 Physical properties of some important metal carbonyl complexes.
Chapter 6
Table 6.1 General organic ligands.
Table 6.2 General organic ligands name and hapticity.
Table 6.3 Bridging carbonyl ligands.
Chapter 8
Table 8.1 Some examples of stable metal carbonyls.
Chapter 9
Table 9.1 List of lanthanides.
Table 9.2 List of actinides.
Chapter 14
Table 14.1 List of different heterogenous catalysis‐based reactions.
Chapter 15
Table 15.1 Classifications in borane clusters.
Table 15.2 Multi‐cluster descriptors.
Chapter 16
Table 16.1 Equilibrium potentials of CO
2
and H
+
reduced products at pH ...
Chapter 17
Table 17.1 The different organometallic compounds are used for pharmaceutic...
Chapter 18
Table 18.1 Highly preferable DFT methods are as follows.
List of Illustrations
Chapter 1
Figure 1.1 General representation of organometallic compound.
Figure 1.2 Bis(benzene)chromium compound.
Figure 1.3 First carbene complex with tungsten.
Figure 1.4 First chromium carbene complex.
Figure 1.5 Zirconocene‐based catalyst.
Figure 1.6 Molybdenum‐based catalyst.
Figure 1.7 Fullerene‐based organometallic compound.
Figure 1.8 First generation Grubbs catalyst.
Figure 1.9 First Si compound.
Figure 1.10 Hexaferrocenylbenzene.
Scheme 1.1 Change in hapticity in Ru compound.
Scheme 1.2 Change in hapticity in Rh compound.
Scheme 1.3 Hapticity in allyl complexes.
Figure 1.11 Metallocene compounds.
Figure 1.12 Dihydrogen complexes.
Figure 1.13 Singlet and triplet state carbene complex.
Chapter 3
Scheme 3.1
Scheme 3.2
Figure 3.1 Classification of organometallic compounds.
Scheme 3.3
Scheme 3.4
Scheme 3.5
Scheme 3.6
Scheme 3.7
Scheme 3.8
Scheme 3.9
Scheme 3.10
Scheme 3.11
Scheme 3.12
Scheme 3.13
Scheme 3.14
Scheme 3.15
Scheme 3.16
Scheme 3.17
Scheme 3.18
Scheme 3.19
Scheme 3.20
Scheme 3.21
Scheme 3.22
Scheme 3.23
Scheme 3.24
Scheme 3.25
Scheme 3.26
Scheme 3.27
Scheme 3.28
Scheme 3.29
Scheme 3.30
Scheme 3.31
Scheme 3.32
Scheme 3.33
Scheme 3.34
Scheme 3.35
Scheme 3.36
Scheme 3.37
Scheme 3.38
Scheme 3.39
Scheme 3.40
Scheme 3.41
Scheme 3.42
Scheme 3.43
Scheme 3.44
Scheme 3.45
Scheme 3.46
Scheme 3.47
Scheme 3.48
Scheme 3.49
Scheme 3.50
Scheme 3.51
Scheme 3.52
Scheme 3.53
Scheme 3.54
Chapter 4
Figure 4.1 Synthesis of Cu(I) complex with cyano by using an electrochemical...
Figure 4.2 Syntheses of [ReClC
p
(H)(dppe)] complex by using electrochemical c...
Figure 4.3 Syntheses of N‐heterocyclic carbine complexes by using electroche...
Figure 4.4 Synthetics of organocopper π‐complexes complexes by using electro...
Figure 4.5 Syntheses of organonickel σ‐complexes [NiBr(Aryl)(bpy)] complex b...
Figure 4.6 Synthesis reactions of organic compounds in the electrochemical c...
Figure 4.7 Synthesis reactions of organic compounds in the electrochemical c...
Figure 4.8 The synthesis reactions of organic compounds in the electrochemic...
Figure 4.9 Representations into the 4 (A, B, C, and D) categorized synthesis...
Figure 4.10 Synthesis of 5‐chloromercuri‐2′‐deoxycytidine.
Figure 4.11 Synthesis of (η
5
‐cyclopentadienyl) dicarbonyliron nucleosides....
Figure 4.12 Synthesis of guanosine derivatives.
Figure 4.13 Synthesis of adenosine derivatives.
Figure 4.14 Synthesis of cyclometallated nucleosides.
Figure 4.15 Synthesis of nucleosides.
Figure 4.16 Synthesis of compounds 310 and 311.
Figure 4.17 Synthesis of nucleosides 333 and 334.
Figure 4.18 Synthesis of η
4
‐butadiene‐tricarbonyliron compounds 363–366.
Figure 4.19 Synthesis of η
4
‐butadiene‐tricarbonyliron compound 371. Reprinte...
Chapter 5
Figure 5.1 Structures of some homoleptic carbonyl complexes.
Figure 5.2 Structures of some heteroleptic carbonyl complexes.
Figure 5.3 Structures of some mononuclear carbonyl complexes
Figure 5.4 Structures of some homonuclear carbonyl complexes.
Figure 5.5 Structures of some heteronuclear carbonyl complexes.
Figure 5.6 Structures of some nonbridged metal carbonyl complexes.
Figure 5.7 Structures of some bridged metal carbonyl complexes.
Figure 5.8 (a) Important reactions of Fe(CO)
5
. (b) Important reactions of Mo...
Figure 5.9 Various modes of bonding of CO.
Figure 5.10 Molecular orbital diagram of CO (i) s and p mixing (ii) s and p ...
Figure 5.11 (i) π‐bonding MO (ii) π*‐antibonding MO.
Figure 5.12 Bonding interactions in CO.
Figure 5.13 Formation of M—C σ‐bond.
Figure 5.14 Formation of π–back bonding.
Figure 5.15 Valence bond resonance structures for M—CO bond order.
Chapter 6
Figure 6.1 Example of organometallic cluster of carbon–metal multiple bond....
Figure 6.2 Example of sandwich organometallic compounds.
Figure 6.3 Example of carbide cluster.
Figure 6.4 Example of Pettit's‐ and Schrock‐type metal complexes.
Figure 6.5 MOT diagram of singlet and triplet carbene.
Figure 6.6 Typical alkylidene complexes.
Figure 6.7 Orbital diagram of Fischer's and Schrock's carbyne.
Figure 6.8 Typical alkylidyne complexes.
Figure 6.9 First synthesized metal–carbene complex.
Scheme 6.1
Scheme 6.2
Scheme 6.3
Scheme 6.4
Scheme 6.5
Scheme 6.6
Scheme 6.7
Scheme 6.8
Scheme 6.9
Chapter 7
Figure 7.1 Structure of ferrocene [1].
Figure 7.2 Molecular orbital diagram and interactions in ferrocene (staggere...
Figure 7.3 Formation of nonsandwich 18‐electron dicyclopentadiene complexes ...
Figure 7.4 Formation of [MCp
2
] [1–3].
Figure 7.5 Erroneous structure of bis‐cyclopentadienyl–iron proposed by Paus...
Figure 7.6 Formation of decaisopropyl ferrocene [1, 13].
Figure 7.7 Formation of [RuCp
2
] [1, 13].
Figure 7.8 Formation of [CoCp
2
] [1, 14].
Figure 7.9 Formation of [FeCp
2
] [1, 15].
Figure 7.10 (a) Different chemical reactions of ferrocene [1, 16]. (b) Diffe...
Figure 7.11 Syn and anti‐isomers of the dibridged derivatives of [FeCp
2
] [1,...
Figure 7.12 Planar metallocenic chirality for 1,2‐ or 1,3‐heterodisubstitute...
Figure 7.13 Some chemical reactions of metallocene of main‐group element (Be...
Figure 7.14 Preparation method of [Cr(η
6
‐C
6
H
6
)
2
] [1, 18].
Figure 7.15 Preparation of metal–bis‐arene sandwich complexes [1, 18].
Figure 7.16 Molecular orbital (MO) diagram of [Cr(η
6
‐C
6
H
6
)
2
] and interaction...
Figure 7.17 Some electrophilic substitution reaction of [Cr(η
6
‐C
6
H
6
)
2
] [1, 1...
Chapter 8
Figure 8.1 Representation of agnostic bond.
Figure 8.2 Different types of metal hydrides.
Figure 8.3 Singlet and triplet carbene.
Figure 8.4 σ‐ and π‐bonding in metal–olefin complex.
Figure 8.5 Various types of metal–alkyne complexes.
Figure 8.6 Different types of η
4
‐C
4
R
4
complexes.
Figure 8.7 Representation of eclipsed and staggered ferrocene.
Chapter 9
Scheme 9.1 Reaction of alkyl lithium with LnCl
3
.
Scheme 9.2 Reaction of CH
3
Li to MCl
3
in THF.
Scheme 9.3 The structure of [Li(L−L)]
3
[M(CH
3
)
6
].
Scheme 9.4 Reaction of LnCl
3
and nNa(C
5
H
5
) and structure of mono‐ and dimeta...
Scheme 9.5 Preparation of organometallic complex of samarium.
Scheme 9.6 Preparation of uranocene.
Scheme 9.7 Preparation of sandwich complexes of actinides.
Scheme 9.8 Preparation of
bis
(arene) organometallic complexes of lanthanides...
Scheme 9.9 Preparation of organometallic complexes of actinides through meta...
Scheme 9.10 Preparation of tris(cyclopentadienyl) lanthanide compounds.
Scheme 9.11 Illustration of σ‐bond metathesis.
Scheme 9.12 Structure of rare earth metal complex prepared through acid–base...
Scheme 9.13 Stoichiometric salt metathesis reactions to form the lanthanide ...
Scheme 9.14 Stoichiometric reaction of lanthanide aryloxides with LiCH
2
SiMe
3
Scheme 9.15 Stoichiometric reaction of lanthanide complexes with benzyl liga...
Scheme 9.16 Salt metathesis reaction between the metal chloride and phenyl l...
Scheme 9.17 Salt metathesis reactions with Ln
3+
chlorides and aryllithiu...
Scheme 9.18 Structure of TmPh
3
(THF)
3
.
Scheme 9.19 Preparation of tris(cyclopentadienyl) systems based on stoichiom...
Scheme 9.20 Structure of CpLnCl
2
(THF)
3
.
Scheme 9.21 Structure of tris(cyclopentadienyl)lanthanide compounds in THF....
Scheme 9.22 Preparation of [U{CH (SiMe
3
)
2
}
3
].
Scheme 9.23 Structure of U{CH(SiMe
3
)
2
}
3
Scheme 9.24 Preparation of salt [Li(TMEDA)]
3
[ThMe
7
].
Scheme 9.25 Structure of uranium (VI) imide.
Scheme 9.26 Formation of intermediate [UCp
*
2
(η
2
‐PhN–NPh)].
Scheme 9.27 Preparation of rare organoimides U(Me‐η
5
Cp)
3
(=NR).
Scheme 9.28 Preparation of [Cp
4
M], [Cp
3
MX], and [CpMX
3
].
Scheme 9.29 Structure of [(η
5
Cp)
4
M], [(η
5
Cp)
3
MCl], and [(η
5
Cp)MCl
3
(THF)
2
].
Scheme 9.30 Selected reactions of [(η
5
Cp)
3
MCl].
Scheme 9.31 Preparation of (η
5
Cp)
3
U through salt elimination route.
Scheme 9.32 Preparation of (η
5
Cp)
3
M through reduction with sodium naphthalen...
Scheme 9.33 Preparation of Th[C
5
H
3
(SiMe
3
)
2
]
3
.
Scheme 9.34 Lability of
bis
(pentamethylcyclopentadienyl) samarium.
Scheme 9.35 Addition reaction of Lewis base (O=CPh
2
) and strongly donating l...
Scheme 9.36 Salt occlusion of alkali halide in organometallic complexes of r...
Scheme 9.37 Structure of η
2
complexes of rare earths having olefins and alky...
Scheme 9.38 Agostic interactions in organometallic complexes of rare earths....
Scheme 9.39 Complex agglomerization in organometallic complexes of rare eart...
Scheme 9.40 Ligand exchange and redistribution reactions in organometallic c...
Scheme 9.41 C—H bond activation in hydrocarbons.
Scheme 9.42 Insertion reactions in organometallic complexes of rare earths....
Scheme 9.43 β‐hydride elimination in organometallic complexes of rare earths...
Scheme 9.44 β‐hydride and β‐alkyl elimination in Cp*
2
LuCH
2
CH(CH
3
)
2
.
Scheme 9.45 oxidation of Cp*
2
Sm(thf)
2
to form an oxo‐bridged dimer in presen...
Scheme 9.46 Formation of lantanoid‐imine azametallacyclopropane complex.
Scheme 9.47 Formation of dinuclear heteroleptic Ce(IV) complex.
Scheme 9.48 Steps involved in hydroamination.
Scheme 9.49 Catalytic hydrogenation using [Cp*
2
LuH] catalyst.
Scheme 9.50 Hydroamination catalyzed by [Cp*
2
La(CH(SiMe
3
)
2
)].
Scheme 9.51 Use of rare earth metal compounds in catalysis of polymerization...
Scheme 9.52 Use of rare earth metal compounds as
c
atalysts and reagents for ...
Chapter 10
Figure 10.1 Structure of (i) coenzyme B
12
5′‐deoxyadenosylcobalamin and (ii)...
Figure 10.2 Reduction of FMN.
Figure 10.3 Active site of nonheme iron–sulfur proteins serving as biologica...
Figure 10.4 Cytochrome c with, on the left, the axial iron ligands: imidazol...
Figure 10.5 Electron transport chain.
Figure 10.6 Cofactor (Mo–Fe‐co) of a nitrogenase enzyme containing the activ...
Chapter 11
Scheme 11.1 Molecular rearrangement upon the dissociaton of CO group.
Scheme 11.2 Replacement of CO ligand by ‐P(CH
3
)
3
.
Scheme 11.3 Binding of NO group.
Scheme 11.4 Internal redox reaction in CoCl
2
L
2
(
lin
‐NO).
Scheme 11.5 Association and dissociation of phosphine in ruthenium complex....
Scheme 11.6 Schematic representation of
Oxidative addition (OA)
and
eductive
...
Scheme 11.7 Reaction between hydrogen and Vaska's complex (
trans
‐IrCl(CO)[P(...
Scheme 11.8 Addition of I
2
to Fe(CO)
5
.
Scheme 11.9 Concerted mechanism of reaction between hydrogen and Vaska's com...
Scheme 11.10
S
N
2
mechanism of reaction between hydrogen and Vaska's complex ...
Scheme 11.11 Free radical mechanism of reaction between hydrogen and Vaska's...
Scheme 11.12 Ionic mechanism of reaction between hydrogen and Vaska's comple...
Scheme 11.13 oxidative addition ofsquare‐planar
d
8
complex
trans
‐Ir(CO)Cl(PE...
Scheme 11.14 C—H activation reaction reported by Bergman.
Scheme 11.15
Schematic representation of
Binuclear oxidative addition.
Scheme 11.16
Example of
Binuclear oxidative addition.
Scheme 11.17 Oxidative addition in iridium complex.
Scheme 11.18 Oxidative addition in platinum complex.
Scheme 11.19 Concerted mechanism of reaction between hydrogen and Vaska's co...
Scheme 11.20 Oxidative addition and reductive elimination in tantalum comple...
Scheme 11.21 Solvation in palladium complex.
Scheme 11.22 Catalytic mechanism of Pd‐catalyzed cross‐coupling reaction.
Scheme 11.23 Three phosphine ligand based
cis
dimethyl complexes of Pd.
Scheme 11.24 Schematic representation of binuclear reductive elimination.
Scheme 11.25 Examples of binuclear reductive elimination.
Scheme 11.26 Schematic representation of insertion reactions.
Scheme 11.27 Schematic representation of 1,1‐ and 1,2‐migratory insertion wi...
Scheme 11.28 Alkyl migration in manganese complexes.
Scheme 11.29 1,1 insertions in manganese complexes.
Scheme 11.30 Examples of 1,2 insertions in HCo(CO)
4
.
Scheme 11.31 Different mechanisms for CO insertion reactions in CH
3
(CO)Mn(CO...
Scheme 11.32 Mechanism 2 versus Mechanism 3 for CO insertion reactions in CH
Scheme 11.33 Mechanism 3 versus Mechanism 2 for manganese complex.
Scheme 11.34 Mechanism of Ziegler–Natta polymerization of alkenes.
Scheme 11.35 Insertion and elimination of olefins into metal hydrides.
Scheme 11.36 Insertion of alkenes in Cp
2
ZrHCl.
Scheme 11.37 insertion of alkenes in Pd‐C bonds of palladium acyl complexes....
Scheme 11.38 insertion into an M–C bond.
Scheme 11.39 Insertion of CO
2
into various M–X bonds.
Scheme 11.40 Schematic representation of Organometallic β‐elimination with e...
Scheme 11.41 Comparison of α and β abstraction.
Scheme 11.42 Example of alpha‐hydrogen abstraction.
Scheme 11.43 Example of alpha‐abstraction in tantalum complexes.
Scheme 11.44 Example of alkyl abstraction.
Scheme 11.45 Mechanism of alkyl abstraction.
Scheme 11.46 Schematic representation of Carbonyl abstraction.
Scheme 11.47 Carbonyl abstraction in iridium compound.
Scheme 11.48 Hydrogen abstraction in chromium complex.
Scheme 11.49 Example of Methyl abstraction.
Scheme 11.50 Silylium abstraction in rhodium complex.
Scheme 11.51 α‐Acyl abstraction in palladium complex.
Scheme 11.52 Mechanism of α‐Acyl abstraction in palladium complex.
Chapter 12
Figure 12.1 (A) Schematic representation of nuclear spin behavior under the ...
Figure 12.2 (a) IR a band (upper) and Raman shifts (lower) for different fun...
Figure 12.3 (a) UV–visible spectra of the Schiff base metal compounds.an...
Figure 12.4 (a) Schematic representation showing SC‐XRD processes such as X‐...
Figure 12.5 (a) Schematic representation of photoemission and relaxation pro...
Figure 12.6 Molecular structure and orientations obtained by ambient tempera...
Chapter 13
Scheme 13.1 Representative hydroboration reaction.
Scheme 13.2 Hydroboration–oxidation.
Scheme 13.3 Oxidation of organoboranes by O
2
.
Scheme 13.4 Mechanism of oxidation reaction.
Scheme 13.5 Carbonylation of organoboranes.
Scheme 13.6 Homologated alcohols and aldehydes.
Scheme 13.7 Carbonylation oxidation of cyclic alkene.
Scheme 13.8 Formation of ketone from carbonylation.
Scheme 13.9 Reduction of organoboranes with carboxylic acid.
Scheme 13.10 Rearrangement followed by reduction.
Scheme 13.11 Rearrangement followed by reduction.
Scheme 13.12 Thioether formation.
Scheme 13.13 Amination.
Scheme 13.14 Reaction of organoborane with α‐haloester.
Scheme 13.15 Representative Suzuki reaction.
Scheme 13.16 Study of mechanism.
Figure 13.1 Catalytic cycle of Suzuki reaction.
Scheme 13.17 Synthesis of biaryls.
Scheme 13.18 Synthesis of biaryls from aryl chlorides.
Scheme 13.19 Suzuki reaction.
Figure 13.2 Carbonylation catalytic cycle.
Scheme 13.20 Amide formation from azide.
Scheme 13.21 Synthesis of amides from
O
‐benzoylhydroxylamine and
O
‐carbamoyl...
Scheme 13.22 Allylation.
Scheme 13.23 Chan–Lam coupling.
Scheme 13.24 Petasis reaction.
Scheme 13.25 Gilman reagent formation.
Scheme 13.26 Types of reactions of organocuprates.
Scheme 13.27 Preparation of homocuprate and heterocuprate.
Scheme 13.28 Reaction of heterocuprate.
Scheme 13.29 Preparation of higher order cyanocuprate.
Scheme 13.30 Substitution reaction by Grignard copper reagent.
Scheme 13.31 Increasing chain length by nucleophilic substitution reaction....
Scheme 13.32 Alkylation at the secondary alkyl halide.
Scheme 13.33 Mechanism of substitution reaction.
Scheme 13.34 Alkylation of allyl acetate.
Scheme 13.35 Reaction with alkenyl halide.
Scheme 13.36 Reaction of organocuprate with acyl halide and thioester.
Scheme 13.37 Epoxide opening.
Scheme 13.38 Conjugate addition.
Figure 13.3 Catalytic cycle for conjugate addition.
Scheme 13.39 Conjugate addition in presence of Lewis acid.
Scheme 13.40 Conjugate addition in presence of electrophile TMSCl.
Scheme 13.41 Conjugate addition followed by trapping by electrophiles.
Scheme 13.42 C‐trapping of reactions.
Scheme 14.43 Synthesis of allenes.
Scheme 13.44 Schematic representation of cross‐coupling reaction of palladiu...
Scheme 13.45 Wacker's process.
Scheme 13.46 Representative Heck reaction.
Scheme 13.47 Heck reaction.
Figure 13.4 Palladium catalytic cycle of Heck reaction.
Scheme 13.48 Representative Negishi coupling.
Scheme 13.49 Negishi coupling.
Figure 13.5 General catalytic cycle for Pd(0)‐catalyzed cross‐coupling react...
Scheme 13.50 Representative Stille coupling.
Scheme 13.51 Examples of Stille coupling.
Scheme 13.52 Representative Kumada coupling.
Scheme 13.53 Kumada coupling.
Scheme 13.54 Representative Hiyama coupling.
Scheme 13.55 Hiyama coupling.
Scheme 13.56 Representative Sonogashira reaction.
Scheme 13.57 Sonogashira reaction.
Scheme 13.58 Representative Butchwald–Hartwig reaction.
Scheme 13.59 Butchwald–Hartwig coupling.
Scheme 13.60 Representative palladium‐catalyzed cyanation reaction.
Scheme 13.61 Cyanation using nontoxic sources.
Scheme 13.62 Representative carbonylation reaction.
Scheme 13.63 Aldehyde generation from carbonylation reaction.
Scheme 13.64 Synthesis of Grignard reagents.
Scheme 13.65 Nucleophilic attack of Grignard reagent on carbon–heteroatom mu...
Scheme 13.66 Miscellaneous reactions of Grignard reagent.
Scheme 13.67 Addition of Grignard reagent on α,β‐unsaturated carbonyl compou...
Chapter 14
Figure 14.1 Steps involved in heterogeneous catalysis.
Chapter 15
Figure 15.1 Representations of molecular and electronic structures of B
x
H
y
[...
Figure 15.2 Crystal structures and numbers of skeletal electron pairs for bo...
Figure 15.3 Synthetic procedure of S and Se‐based heteroborane clusters [7]....
Figure 15.4 Synthesis schema of some carboranes.
Figure 15.5 Preparation of some carboranes clusters.
Figure 15.6 Some reactivity properties of cluster compounds of heteroboranes...
Figure 15.7 Some nucleophilic reactions of heteroboranes. (b) for
9
−
: ...
Figure 15.8 The interactions of the carborane cluster with the estrogen rece...
Figure 15.9 Synthesis of some metallaborane clusters.
Figure 15.10 Synthesis of some metallaborane clusters (Fe, Mo, Ta, Nb, Ru, a...
Figure 15.11 Some reactions of metallaboranes [22].
Chapter 16
Scheme 16.1 CO
2
fixation by bismuth compounds containing Bi‐O bonds.
Figure 16.1 Schematic of reduction of CO
2
.
Scheme 16.2 Terpyridyl nickel complexes employed in CO
2
−
reduction.
Scheme 16.3 Cyclam based nickel complexes in CO
2
reduction.
Scheme 16.4 Mononuclear and dinuclear nickel modified macrocyclic ligands in...
Scheme 16.5 Iron complexes with (
tbu
dhbpy)‐ligand system in reducing CO
2
to ...
Scheme 16.6 Iron complexes with cyclopentadienone ligand system in reduction...
Scheme 16.7 Copper complex employed with quaterpyridine ligand in CO
2
reduct...
Scheme 16.8 Cobalt complexes with varying ligand systems for CO
2
reduction....
Scheme 16.9 Cobalt complexes bearing pyridylmonoimine ligand with varying li...
Scheme 16.10 Pincer based palladium complexes for reduction of CO
2
.
Scheme 16.11 Palladium complexes with varying alkyl chains employed in CO
2
r...
Scheme 16.12 Ruthenium‐NHC complexes in CO
2
reduction.
Scheme 16.13 Pincer based nickel‐NHCs in CO
2
reduction.
Scheme 16.14 Iron‐NHC complexes employed in CO
2
reduction.
Scheme 16.15 Manganese NHC complexes employed in CO
2
reduction.
Figure 16.2 Illustration of the flexible behaviors of MOFs on interacting wi...
Figure 16.3 Cross section of the open channel present in [Er(PDA)
1.5
]; (Top)...
Chapter 17
Figure 17.1 The different applications of organometallic compounds.
Figure 17.2 The properties of organometallic compounds.
Figure 17.3 The last five years of developments in organometallic compounds ...
Chapter 18
Figure 18.1 Structure of transition metal complexes obtained through DFT met...
Figure 18.2 Transition metal complexes developed through DFT methods by grou...
Scheme 18.1 Calculated dissociation energies for reaction transition‐metal c...
Scheme 18.2 C(sp
3
)–H activated Pd‐catalyzed thorough anionic bis(bicarbonate...
Scheme 18.3 Meta‐selective C–H activation reactions: (a) nitrile directing g...
Scheme 18.4 Ligand size determine the ligation state of activated Pd [72, 73...
Scheme 18.5 (a) Bis‐ligated mechanism of Suzuki–Miyaura coupling, where L = ...
Scheme 18.6 Demonstration of (a) Boronate and (b) Hydroxo mechanisms of Suzu...
Figure 18.3 Regioselectivity of Mizoroki–Heck coupling, which depends upon
t
Scheme 18.7 Oxidative addition reaction of Ni with aryl bromides and chlorid...
Scheme 18.8 Coordination reaction of Grignard reagent with Ni complex by hyd...
Scheme 18.9 Catalytic cycle of Ni‐catalyzed coupling reaction of alkyne–alde...
Scheme 18.10 Regioselective Ni‐catalyzed alkyne–aldehyde coupling.
Scheme 18.11 Activation of Ni‐catalyzed Ar—OBz and ArO—Bz Bond.
Scheme 18.12 Ni‐catalyzed [3+2+2] cycloaddition of cyclopropylidene acetate ...
Scheme 18.13 Hydrosilylation of allenes with Ni/IPr or Pd/IMes Systems.
Figure 18.4 Demonstration of transition‐metal catalyzed hydrogenations [117]...
Scheme 18.14 Reactivity of α‐diazocarbonyl compounds: (a) increasing the ten...
Scheme 18.15 Mechanism of Rh‐catalyzed [5+2] cycloaddition of vinyl cyclopro...
Scheme 18.16 Demonstration of mechanism of Rh‐catalyzed intramolecular [3+2]...
Scheme 18.17 (a) M–L weakens hydrogen bond and facilitates hydrogen cleavage...
Scheme 18.18 (a) Ru‐catalyzed hydrogenation [141, 142]; (b) transition‐metal...
Scheme 18.19 Ir‐catalyzed, activation of phosphine‐assisted C–F.
Scheme 18.20 Ir‐catalyzed intramolecular [5+2] cycloaddition of vinylcyclo p...
Guide
Cover
Table of Contents
Title Page
Copyright
Preface
About the Editors
Begin Reading
Index
End User License Agreement
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Organometallic Compounds
Synthesis, Reactions, and Applications
Edited byDakeshwar Kumar VermaJeenat Aslam
Editors
Dr. Dakeshwar Kumar VermaGovt. Digvijay Autonomous PG CollegeDepartment of ChemistryRajnandgaon, Chhattisgarh491441 ChhattisgarhIndia
Dr. Jeenat AslamTaibah UniversityDepartment of ChemistryYanbu30799Saudi Arabia
Cover Image: © Stampf/pixabay
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Print ISBN: 978‐3‐527‐35178‐7ePDF ISBN: 978‐3‐527‐84092‐2ePub ISBN: 978‐3‐527‐84093‐9oBook ISBN: 978‐3‐527‐84094‐6
Preface
The present edited book titled Organometallic Compounds: Synthesis, Reactions, and Applications discusses the basics, current trends, challenges, and future prospects, showing the value and scope of organometallic compounds toward current applications. This edited book will be carefully written to present a modern account of traditional methods and the latest details of recent advances in organometallic chemistry. The edited book will contain a traditional and logical approach in detail about introduction, nomenclature, synthesis methods, current applications, metallocenes, natural organometallic compounds, emerging role of organometallic compounds, F‐block‐based organometallic compounds, toxicity and applications of computational modeling for organometallic compounds. The book will be of significant interest to students of chemistry, pharmacy, biochemistry, and chemical engineering at the advanced undergraduate, graduate, and postgraduate levels, as well as academic and industry researchers who wish to familiarize themselves with the concepts and applications of organometallic chemistry. A book to wrap the developments in detailed synthetic reaction mechanisms and industrial applications is long overdue, and the present one will be a milestone in the field.
This will be the only book that provides chronological advancements of organometallic compounds (both synthetic and natural), their synthesis mechanisms, and recent industrial applications in the fields of material science, engineering, and science. The book will also serve as a valuable source for new learners about fundamentals, basics, reactions, catalytic mechanisms, and modern applications such as carbon dioxide fixation, reduction, gas adsorption and gas purification, drug delivery, renewable energy, and waste water treatment. It serves as a valuable reference for scientists, organochemists, biochemists, pharmacists, and engineers who are searching information on organometallic compounds, their current applications, toxicity, and computational modeling.
To confine the comprehensive description of organometallic compounds and to propose a rational and expressive design of the topic and a concentrated up‐to‐date reference, the book is divided into many chapters. Topics covered in Chapters 1–4 are fundamental aspects, nomenclature, classification properties, and synthesis methods of organometallic compounds. Chapter 5 explains the metal carbonyls' synthesis, properties, and structure. Chapter 6 covers metal‐carbon multiple‐bonded compounds. Chapter 7 describes the metallocenes' synthesis, properties, and structure. Chapter 8 explains σ‐complexes, p‐complexes, and ηn‐CnRn carbocyclic polyenes‐based organometallic compounds. Chapter 9 covers the organometallic complexes of the lanthanoids and actinoids. Chapter 10 describes bio‐organometallic chemistry. Chapter 11 explains the important reactions of organometallic compounds. Chapter 12 shows the characterization techniques of organometallic compounds. Chapter 13 discusses the organometallic compounds based on important reagents. Chapter 14 covers homogeneous and heterogeneous catalysis by organometallic complexes. Chapter 15 explains the cluster compounds boranes, heteroboranes, and metallaboranes. Chapter 16 covers the applications of organometallic compounds for carbon dioxide fixation, reduction, gas adsorption, and gas purification. Chapter 17 shows the emerging role of organometallic compounds for drug delivery, renewable energy, and waste water treatment. Chapter 18 explains the toxicity of organometallic compounds. Chapter 19 describes the computational approaches for some important organometallic catalysis reactions.
This book aims to deliver the recent evidences from fundamentals and synthesis to applications on organometallic compounds. The book will be intended for a very broad audience working in the fields of organic synthesis, environmental science and engineering, nanotechnology, energy, chemistry, etc. This book will be a valuable reference source for libraries in universities and industrial institutions, government and independent institutes, individual research groups, and scientists working in the field. Overall, this will be a valuable reference for government and non‐government agencies, research scholars of the field, teachers and research supervisors, policy makers, organometallic‐compounds‐related industries, chemists and chemical engineers working in both R&D and academia who want to learn more on fundamental aspects of organometallic chemistry. The book will be a valuable source and guidebook for science (B. Sc. and M. Sc.), environmental science, pharmaceuticals, biomedical engineering, and engineering (B. Tech. and M. Tech.) students to learn the basics of recent evidences on the proposed title.
The editors and contributors of all chapters are well‐known researchers, scientists, and experts from academia and industry.
On behalf of John Wiley & Sons, Inc., we thank all contributors for their exceptional and whole‐hearted contribution. Invaluable thanks to Dr. Sakeena Quraishi (Associate Commissioning Editor), Miss Katherine Wong (Senior Managing Editor), and the Editorial Team at John Wiley & Sons, Inc. for their wholehearted support and help during this project. In the end, all appreciation to John Wiley & Sons, Inc. for publishing the book.
02 September 2022
Dakeshwar Kumar Verma
Govt. Digvijay AutonomousPostgraduate CollegeRajnandgaon, Chhattisgarh,491441, India
Jeenat Aslam
Department of Chemistry,College of Science, Taibah UniversityYanbu‐30799, Al‐Madina, Saudi Arabia
About the Editors
Dakeshwar Kumar Verma, PhD, is an Assistant Professor of Chemistry at Govt. Digvijay Autonomous Postgraduate College, Rajnandgaon, Chhattisgarh, India. His research is mainly focused on the preparation and designing of organic compounds for various applications and green chemistry. Dr. Verma is the author of more than 60 research papers, review articles, and book chapters in peer‐reviewed international journals of ACS, RSC, Wiley, Elsevier, Springer, Taylor & Francis, etc. He has also worked as an editor/co‐editor/author on various books published by Elsevier, Wiley Science, and De Gruyter. He has more than 870 citations with an H‐index of 16 and an i‐10 index of 21. Recently, two full‐time Ph.D. research scholars have been working under his guidance. Dr. Verma received a Council of Scientific and Industrial Research Junior Research Fellowship award in 2013. He also availed the MHRD National Fellowship during his Ph.D. in 2013.
Jeenat Aslam, PhD, is currently working as an Associate Professor at the Department of Chemistry, College of Science, Taibah University, Yanbu, Al‐Madina, Saudi Arabia. She obtained her PhD in Surface Science/Chemistry at the Aligarh Muslim University, Aligarh, India. Her research is mainly focused on materials and corrosion, nanotechnology, and surface chemistry. Dr. Jeenat has published several research and review articles in peer‐reviewed international journals of ACS, Wiley, Elsevier, Springer, Taylor & Francis, Bentham Science, etc. She has authored/edited many books and has contributed to twenty‐seven book chapters.
1Organometallic Compounds: The Fundamental Aspects
Geetha B. Markandeya and Srinivasa Budagumpi
Jain University, Centre for Nano and Material Sciences, Jain Global Campus, 45 km, NH – 209, Jakkasandra Post, Kanakapura Taluk, Ramanagaram 562112, Bangalore, Karnataka, India
1.1 Introduction
1.1.1 Organometallic Chemistry
The branch of chemistry deals with the study of molecules having a metal–carbon bond, in which a compound is said to be an organometallic compound when the metal–carbon bond in a molecule should be completely or partially covalent. Depending upon the elements in the periodic table, organometallic chemistry is mainly classified into main groups metal, transition metal, lanthanide, and actinide‐based organometallics.
1.1.2 Organometallic Compounds
The organic compounds contain at least one metal–carbon bond in which metal is directly attached to the carbon atom in which there should be a bonding interaction (covalent, ionic, localized/delocalized) between the metal and the carbon atom are defined as organometallic compounds. The metals may be alkaline metals, alkaline earth metals, and metalloids (boron, silicon, arsenic, germanium, tellurium, and selenium). The bond present between the metal atom and the carbon is likely covalent in nature.
Examples: Organocadmium compounds, organoboron compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, organolead compounds, and organotin compounds.
1.1.3 Structure of Organometallic Compound
The nature of the metal–carbon bond varies from ionic to covalent. The organometallic compounds have some effect on the nature of metal–carbon and these compounds have both organic and metal portions in which the metallic portion has greater importance. The electropositive nature of metal will be the ionic nature of the metal–carbon bond.
In organometallic compounds, the carbon is bonded to an electropositive atom, which has a negative charge, whereas the metal has a slightly positive charge; hence, the organometallic compounds having the organic part behave as nucleophilic or basic as shown in Figure 1.1.
Figure 1.1 General representation of organometallic compound.
1.2 Milestones in Organometallic Compounds
In 1760, the first organometallic compound of the main group (Eq. (1.1)), cadet fuming liquid was discovered. In the Paris military pharmacy, a cadet discovered a fuming liquid while working on ink while preparing cobalt salt from cobalt minerals consisting of arsenic, which is called cacodyl(malodorous)oxide [1, 2].
1.2.1 Equation (1.1): Synthesis of First Organometallic Compound
In 1827, W. C. Zeise, a Danish pharmacist, discovered the first organometallic compound with a transition metal called Zeise's, K[PtCl3C2H4]H2O. When K2PtCl4 was refluxed in ethanol, it resulted in the formation of Zeise's salt (Eq. (1.2)). It was characterized as the first organometallic olefin complex. Herein, they have used platinum because the Nobel metal complexes are stable toward air and moisture [3, 4].
1.2.2 Equation (1.2): Preparation of Zeise's Salt
In 1849, Edward Frankland prepared diethylzinc (a pyrophoric liquid), while trying to prepare an ethyl radical, he ended up with ethylzinc iodide (solid) and diethylzinc (liquid) [5, 6]. Whereas in 1852, he used sodium amalgam and methyl halide to prepare dimethyl mercury. Furthermore, many people have used R2Hg and R2Zn following an alkyl transfer reaction to prepare main group elements of organometallic compounds.
In the same year 1852, Schweizer and Lowig used an alloy of Na/Pb to prepare tetraethyllead (Eqs. (1.3) and (1.4)). In 1863, organochlorosilane was prepared by Friedel and Craft using alkylzinc as a reagent (Eq. (1.5)).
1.2.3 Equations (1.3)–(1.5): Preparation of Organochlorosilane Compound
In 1868, [PtCl2(CO)]2 the first metal carbonyl compound (Eq. (1.6)) was prepared by Schutzenberger [7].
1.2.4 Equation (1.6): Synthesis of First Metal Carbonyl Compound
In 1890, Ludwig Mond prepared the first binary metal carbonyl Ni(CO)4 (Eq. (1.7)), which is used for the refining of nickel [8–10].
1.2.5 Equation (1.7): Synthesis of First Binary Metal Carbonyl Complex
In 1899, the Philippe Barbier, Grignard's teacher introduced Barbier reaction (Eq. (1.8)). It was a one pot reaction carried out in the presence of water. Compared to Grignard reaction this is less versatile.
1.2.6 Equation (1.8): Barbier Reaction
Whereas in 1900, in RMgX, Zn was replaced by Mg in Barbier by Grignard and called as Grignard reagent (Eq. (1.9)). This reagent is more versatile than the Barbier reaction and has more applications compared to organozinc reagents [11].
1.2.7 Equation (1.9): Synthesis of Organic Compound Using a Grignard Reagent
In 1912, P. Sabatier and V. Grignard were awarded the Nobel Prize for Grignard reagent, and they followed Sabatier's method for the hydrogenation by using metal powders.
In 1917, the first alkyllithium derivatives (Eqs. (1.10) and (1.11)) were prepared by Wilhelm Schlenk, and he followed the transalkylation of organomercury compounds. Whereas the synthetic strategies of lithium derivatives replace the Grignard reagent as the primary anionic intermediate (1.10).
1.2.8 Equations (1.10) and (1.11): Synthesis of Alkyllithium Compound
In 1921, Thomas Midgley introduced tetraethyllead as an additive in gasoline while working on GE motors [12].
In 1930, K. Ziegler prepared organolithium compounds (Eqs. (1.12) and (1.13)) by a simple synthetic procedure and, furthermore, fine‐tuned by Gilman. Later on, this compound was widely used.
1.2.9 Equations (1.12) and (1.13): Synthesis of Organolithium Compound
In 1938, hydroformylation (Eq. (1.14)) was discovered by Otto Roelen, for the first time in homogeneous catalysis an organometallic compound has been used [13, 14].
1.2.10 Equation (1.14): Hydroformylation Reaction
In 1943, direct synthesis of organochlorosilane (Eq. (1.15)) was discovered by E G Rochow, further it initiated for large scale production of silicones [15].
1.2.11 Equation (1.15): Synthesis of Organochlorosilane Compound
In 1948, acetylene trimerization (Eq. (1.16)), which was catalyzed by nickel was discovered by W. Reppe [16].
1.2.12 Equation (1.16): Trimerization of Acetylene
In 1951, the sigma bonded structure of ferrocene (Eq. (1.17)) was suggested and independently prepared by two groups. Fischer, Woodward, and Wilkinson proposed the sandwich structure of ferrocene [17].
1.2.13 Equation (1.17): Synthesis of Ferrocene
In 1955, W. Hafner and E. O. Fischer followed rational synthesis to prepare bis(benzene)chromium (Figure 1.2), even though in 1919 same reaction was carried by F. Hein with CrCl3 and PhMgBr [18, 19].
Figure 1.2 Bis(benzene)chromium compound.
In 1955, G Natta and K Ziegler used a mixed metal catalyst to develop olefin polymerization at lower pressure.
In 1959, the stabilization of cyclobutadiene was done by complexation in [(C4Me4)NiCl2]2.
In 1961, Vaska's complex was discovered, which binds reversibly to O2 trance IrCl(CO)(PPh3)2[20].
In 1963, Ziegler and Natta both were awarded Nobel prize for Ziegler Natta catalyst.
In 1964, the first carbene complex with metal W (tungsten) (Figure 1.3) by E. O. Fischer [21].
Figure 1.3 First carbene complex with tungsten.
In 1965, Coffey and Wilkinson, for hydrogenation of alkenes, they have used (PPh3)3RhCl as a homogeneous catalyst [22].
In 1968, asymmetric catalysis (Eq. (1.18)) was discovered by William S. Knowles, the achiral substrates can be converted into chiral products with the help of complexes consisting of ligands that are chiral with high enantiomers [23].
1.2.14 Equation (1.18): Asymmetric Catalysis Reaction
In 1972, T Mizorki and R. F. Heck discovered the substitution reaction of aryl halides with vinylic hydrogen atom a palladium based catalysis reaction [24].
In 1973, the first Chromium carbene complex (Figure 1.4) was prepared by E. O. Fischer. In the same year G. Wilkinson and E. O. Fischer were awarded Nobel Prize for working on metal sandwich compound [25].
Figure 1.4 First chromium carbene complex.
In 1976, M. F. Lappert prepared first double bonded compound tin–tin using dimetallenes first main group element [26].
In 1979, the first paper on palladium catalyzed Suzuki coupling reaction (Eq. (1.19)) of aryl boronic acids was published by Suzuki and Miyaura [27].
1.2.15 Equation (1.19): Palladium Catalyzed Suzuki Coupling Reaction
In 1980, the zirconocene‐based catalyst (Figure 1.5a,b) was prepared by Walter Kaminsky only for syndiotactic and isotactic polypropylene.
Figure 1.5 Zirconocene‐based catalyst.
In 1981, the compound having Si=Si (silicon–silicon double bond) was prepared by Robert West [28].
In 1990, for olefin metathesis, a molybdenum‐based catalyst (Figure 1.6) was discovered by Richard Schrock [29].
Figure 1.6 Molybdenum‐based catalyst.
In 1991, the fullerene‐based organometallic compound (Figure 1.7) was made by J. M. Hawkins, which is also the derivative of structurally characterized fullerene C60(OsO4)(4‐t‐BuPy)2. Furthermore, the organometallic compounds with η2‐bonding directly with metal–carbon bonds were discovered [30].
Figure 1.7 Fullerene‐based organometallic compound.
In 1995, the olefin metathesis catalyst, also called first‐generation Grubbs catalyst (Figure 1.8), was prepared by Robert Grubbs [31].
Figure 1.8 First generation Grubbs catalyst.
In 1997, the organometallic compound having C atom as a ligand was showed by C C Cummins [(R2N)3MoC]−. In the same year G. M. Robinson prepared the salt of sodium Na2[ArGaGaAr] and postulated [32, 33].
In 2001, for asymmetric hydrogenation, W. S. Knowles, K. B. Sharpless, and R. Noyori received Nobel Prize.
In 2002, the molecular hybrids of fullerene and ferrocene together called bucky ferrocene (Eq. (1.20)) was prepared by E. Nakamura by treating [FeCp(CO)2]2 with C70HMe3 or C60HMe5[34].
1.2.16 Equation (1.20): Synthesis of Bucky Ferrocene
In 2004, the preparation and structural characterization of first Si–Si (Figure 1.9, Si—Si triple bonded) molecule was done by A. Sekiguchi [35].
Figure 1.9 First Si compound.
In the same year 2004, the first zinc organometallic compound Zn2(Cp)2 was prepared by E Carmona [36].
In 2005, for olefin metathesis R. R. Schrock, Y. Chauvin, and R. H. Grubbs, received Nobel Prize. In the same year, the first stable organometallic compound with quintuple bond was prepared by P. Power [37].
In 2006, hexaferrocenylbenzene (Figure 1.10) was prepared by P. C. Vollhardt [38].
Figure 1.10 Hexaferrocenylbenzene.
1.3 Stability of Organometallic Compounds
The oxidation of the organometallic compounds will plays a vital role in the stability of the compounds, whereas the organometallic compounds are thermally unstable due to the negative free energy of carbon dioxide, metal oxide, and water production. In addition to that, at lower room temperatures, the organometallic compounds are unstable to oxidation due to the presence of empty orbitals of metal or due to nonbonding electrons [39].
The hydrolysis of organometallic compounds will also affect the stability of compounds
Hydrolysis involves the reaction of nucleophilic attack of water.
The rate of hydrolysis is determined by the polarity of the metal–carbon bond, the higher the polarity of the metal–carbon bond, the faster will be the rate of hydrolysis.
1.4 Properties of Organometallic Compounds
Most organometallic compounds with aromatic and hydrocarbon groups are solid.
The metal–carbon bond is covalent.
Organometallic compounds with metals such as lithium and sodium are volatile and burn spontaneously.
Organometallic compounds having electropositive metals behave as reducing agents.
Organometallic compounds are toxic to human beings in most cases.
Organometallic compounds have low melting point.
Organometallic compounds are soluble in ether, whereas insoluble in water.
Organometallic compounds are very reactive compounds.
The electronegativity of carbon in organometallic compound is 2.5 and for metals the electronegativity is below 2.0.
Many organometallic compounds occur in solid state, particularly the compounds having hydrocarbons and aromatic groups. Few of organometallic compounds are liquids and gases.
1.5 Basic Concepts in Organometallic Compounds
(1) 18‐electron rule
(2) Π – back bonding or back donation
(3) Hapticity
1.5.1 18‐Electron Rule
The structure and bonding present in the organometallic compound are studied based on the 18‐electron rule and this is the combination of the ability of the ligand for pi acceptor or sigma donor and the back bonding and bonding nature of the ligand. In addition to that, the stability of the metal complexes is predicted and characterized by the 18‐electron rule. A total of 18 electrons are present in the valence shell of MT, whereas a total of 10 electrons in the d orbital (2 each from five d orbitals), 6 electrons from the p orbital (2 each from three p orbitals) and 2 electrons from 1 s orbital. The combination of these atomic orbitals (5d+3p+1s) results in 9 molecular orbitals. These 9 molecular orbitals are metal–ligand non–bonding or bonding orbitals, and there might be a few higher energy antibonding molecular orbitals. These 9 molecular orbitals are filled by electrons originating from ligand or metal [39].
1.5.1.1 Statement of 18 Electron Rule
Thermodynamically stable transition metal organometallic compounds are formed when the sum of the metal d electrons and the electrons conventionally considered as being supplied by the surrounding ligands equals 18. In this way, the metal attains the electronic configuration of the next higher Nobel gas in general ns2 (n−1)d10 np6. It is also called the EAN (effective atomic number) rule or inert gas rule [39].
The presence or absence of a metal–metal bond and the stability of the complex can be determined by counting the number of electrons surrounded in the outer shell of the metal atom in the complex.
Two methods were used for counting the electrons
Neutral atom counting method–it is difficult for organometallic compounds because it doesn't require oxidation state assignment
Oxidation state/ionic counting method in this method a change in the oxidation state of the metal is required.
In 1921, Irwing Langmuir formulated the 18‐electron rule and derived the equation.
where
V
c
=
number of shared electrons in a metal complex or compound.
s
=
number of electrons for the completion of the valence shell.
e
=
number of valence electrons in an isolated atom.
In organic chemistry, the compounds have to obey the octet rule, the value of s is 8.
For Example, NH3, 3 = 8−5
In organometallic complexes, such as transition metal carbonyls, the value of s is 18.
Example, Ni(CO)4, 8 = 18−10, Cr(CO)6, 12 = 18−6
1.5.1.2 Examples
(1) TiCl
4
Electronic configuration: 3s23p63d24s2
By neutral counting method: for Ti 4 electron, for Cl 1 electron:
By oxidation/ionic counting method: for Ti4+ 0 electron, for Cl 2 electron
TiCl4 is having only 8 electrons, but it should be 18 electrons to satisfy 18‐ electron rule. TiCl4 will act as good Lewis acid and it reacts with alcohol, water and amines.
(2) Fe(CO)
5
Electronic configuration: 3s23p63d64s2
By neutral counting method: for Fe 8 electron, for CO 2 electron:
By oxidation/ionic counting method: in this case all the fragments are neutral in nature.
This is a stable compound with 18‐electron complex.
(3) Fe(C
5
H
5
)
2
or FeCp
2
Electronic configuration: 3s23p63d64s2
By neutral counting method: for Fe 8 electron, for C5H5 2 electron:
By oxidation/ionic counting method: for Fe2+ 6 electron, for C5H5 2(6) = 12 electron
This is a stable compound with 18‐electron complexes.
(4) [CpFe(CO)
2
]
2
Neutral counting method
Electrons were counted for only one iron center since the other iron will contribute one electron.
(5) CpFe(CH
3
)(CO)
2
Neutral counting method
(6) Fe
2
(CO)
9
Neutral counting method
1.5.2 Π –Back Bonding or Back Donation
When electrons move from one atomic orbital to another anti–bonding orbital π* of a ligand or atom in the process relieves the metal that has an excess negative charge.
Example: Zeise's salt, Ni(CO)4.
1.5.3 Hapticity ηx
The term hapticity is defined as total number of donor atoms of a ligand that are coordinated (attached) to the central metal atom (it is also defined as how a contiguous group of atoms of a ligand, which are coordinated to the central metal atom).
Hapticity is denoted by a Greek word ηx.
Where, x – number of donor atoms attached to the metal.
1.6 Hapticity of Ligands
Ligands are an atom or group of atoms, ions, or molecules that are capable of donating a pair of electrons to the metal atom and are called ligands.
The hapticity of ligands ranges from 1 to 8 that is monohapto ligands to octohapto ligands.
(1) Monohapto ligands η
1
: these are the ligands joined with one atom and it has the capacity to donate one electron (1 electron donor ligands).
Examples: Alkyl groups(–CH3) (M–CH3), Aryl(–C6H5), Alkenyl(M–CR=CR2) (where R2‐alkyl)
ηx = η1 number of donor atoms.
(2) Dihapto ligands η
2
: Two ligands atoms are directly bonded to metal (2 electron donor ligands).
Examples: Alkenes (=CH2=CH2=), Zeise's salt(K[PtCl3C2H4]H2O)
(3) Trihapto ligands η
3
: three atoms of the ligands are directly bonded to metal atom (three‐electron donor). There are two types of complexes, π‐allyl complexes and σ‐allyl complexes.
ηx = η3 number of donor atoms.
π‐allyl complexes: when π‐bond will be delocalized around all the three carbon atoms time to time. The π‐allyl complexes are 3 electron donor complexes.
σ‐allyl complexes: when metal is directly attached to one carbon atom of the ligand.
(4) Tetrahapto ligands η
4
: these are the ligands joined with four atoms and it has the capacity to donate 4 electrons.
Example: Cyclobutadiene it has delocalized electron around all the four–carbon atom.
(5) Pentahapto ligands η
5
: these are the ligands joined with five atoms and it has the capacity to donate 5 electrons.
Example: Ferrocene bis[η5‐cyclopentadienyl]iron
(6) Hexahapto ligands η
6
: these are the ligands joined with six atoms and it has the capacity to donate 6 electrons.
Example: benzene
(7) Heptahapto ligands η
7
: these are the ligands joined with seven atoms and it has the capacity to donate 7 electrons.
(8) Octahapto ligands η
8
: these are the ligands joined with eight atoms and it has the capacity to donate 8 electrons.
Example: Uranocene‐bis(η8‐1,3,5,7‐cyclooctatetraene)uranium.
1.7 Change in Hapticity
During the course of the reaction the hapticity of the ligand changes (Schemes 1.1 and Scheme 1.2).
Scheme 1.1 Change in hapticity in Ru compound.
Scheme 1.2 Change in hapticity in Rh compound.
The η5‐Cp changes to η3‐Cp, by making room on the metal where one molecule of CO is removed and ligand L is donating extra two more electrons.
The hapticity will changes the electron count.
Hapticity will change for dienes, indenyl and it will change for cyclopentadienyl for some time.
Hapticity does not change the oxidation state.
It makes a path for a system “giving room” for other reactions or it will avoid electron counts above 18 electron.
1.8 Hapticity Verses Denticity
Table 1.1 Differences between hapticity verses denticity[40].
Hapticity
Denticity
Hapticity refers to how a contiguous group of atoms of a ligand is coordinated to the central metal atom
It is denoted by η.
The contiguous atoms are involved in the coordination process.
Ferrocene where the iron(Fe) is sandwiched between two hydrocarbon rings.
Denticity refers to the number of donor atoms in the same ligand that binds to the central metal atom in the coordination complex.
It is denoted by k.
The donor atoms will attach to the central metal atom.
EDTA coordinated to central metal atom through six atoms two nitrogen and the other four oxygen.
1.9 Counting of Electrons and Finding out Metal–Metal Bonds
Metal carbonyl clusters are the compounds that contain metal in the lower oxidation state, these compounds also consist of metal–metal bonds. The larger and structurally complex clusters come under this category. The total number of metal–metal bonds and the number of bonds present in one metal to the other metal in a complex cluster can be determined by following the procedure and this holds good for the complexes with nuclearity ≤ 4. The electronic structure of the complex can be understood by the bond between the metal atoms, whereas each metal atom has to attain 18 electronic configurations [39].
1.9.1 Calculating the Number of Metal–Metal Bonds
First, find out the total number of valence electrons in the molecule and consider it as X.
Let us consider an equation, Y = (
n
X8)‐X, where “
n
” is the number of metals present in the complex.
Y/2 is the number of metal–metal bonds present in the complex.
X/2 is the number of electrons per metal. If the number of electrons is equal to 18, that shows there is no metal–metal is present. If the number of electrons is equal to 17, it shows one metal–metal bond is present. If the number of electrons is equal to 16, two metal–metal bonds are present.
1.9.2 Writing the Probable Structure of Compound
The first step is to write the metal core(center)
The ligands and metal carbonyls can be arranged to the metal core in which the metal core has to satisfy the 18‐electron rule, additionally the carbonyl group has to occupy either a bridged or terminal position.
1.9.3 How to Draw the Probable Structure of Ni(η1‐C3H5) (η3‐C3H5)
1.9.4 How to Draw the Probable Structure of (μ‐CO)‐[η5‐CpRh]3(CO)
Total valence electron = 4 + [(6 + 8)X3] + 2 = 48
The number of metal–metal bond = (3X8)−48 = 6/2 = 3
Number of bonds per metal center = 2 (48/3 = 16)
1 and 2 are the plausible structure of (μ‐CO)‐[η5‐CpRh]3(CO). Among 1 and 2 structures, 1 is proper, whereas, in structure 2, the electron count on metal 3Rh is found to be 17, 18, and 19e−, but it should be 16.
The 18e− rule is not applicable for all the f–block elements, there are exceptions to transition metal organometallics. The 18e− rule for organo–transition metal compounds can be explained by various physical and chemical properties.
From 18e− rule, one can predict the total number of ligands coordinated to a particular metal and also the reactivity/stability of the complex. This method holds good for the metals having low valency and also with the small ligands that are strong sigma donors and π–acceptors. The ligands are small enough that allow metal that coordinates saturated and that give more ligand field splitting value. 18e− are required to fill the dπ orbitals similar to the octet rule. There are some exceptions to 18e− rule also few of them are mentioned below.
Metals having d
8
electrons: the metals having d
8
electrons have the tendency to form a square planar complex with 16e
−
