The Chemical Bond E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1098

Veröffentlichungsjahr: 2014

Beschreibung

A unique overview of the different kinds of chemical bonds that can be found in the periodic table, from the main-group elements to transition elements, lanthanides and actinides. It takes into account the many developments that have taken place in the field over the past few decades due to the rapid advances in quantum chemical models and faster computers. This is the perfect complement to "Chemical Bonding - Fundamentals and Models" by the same editors, who are two of the top scientists working on this topic, each with extensive experience and important connections within the community.

Leseprobe

Table of Contents

Cover

Related Titles

Title Page

Copyright

Preface

List of Contributors

Chapter 1: Chemical Bonding of Main-Group Elements

1.1 Introduction and Definitions

1.2 The Lack of Radial Nodes of the 2p Shell Accounts for Most of the Peculiarities of the Chemistry of the 2p-Elements

1.3 The Role of the

Outer

d-Orbitals in Bonding

1.4 Secondary Periodicities: Incomplete-Screening and Relativistic Effects

1.5 “Honorary d-Elements”: the Peculiarities of Structure and Bonding of the Heavy Group 2 Elements

1.6 Concluding Remarks

References

Chapter 2: Multiple Bonding of Heavy Main-Group Atoms

2.1 Introduction

2.2 Bonding Analysis of Diatomic Molecules E

2

(E = N – Bi)

2.3 Comparative Bonding Analysis of N

2

and P

2

with N

4

and P

4

2.4 Bonding Analysis of the Tetrylynes HEEH (E = C – Pb)

2.5 Explaining the Different Structures of the Tetrylynes HEEH (E = C – Pb)

2.6 Energy Decomposition Analysis of the Tetrylynes HEEH (E = C – Pb)

2.7 Conclusion

Acknowledgment

References

Chapter 3: The Role of Recoupled Pair Bonding in Hypervalent Molecules

3.1 Introduction

3.2 Multireference Wavefunction Treatment of Bonding

3.3 Low-Lying States of SF and OF

3.4 Low-Lying States of SF

2

and OF

2

(and Beyond)

3.5 Comparison to Other Models

3.6 Concluding Remarks

References

Chapter 4: Donor–Acceptor Complexes of Main-Group Elements

4.1 Introduction

4.2 Single-Center Complexes EL

2

4.3 Two-Center Complexes E

2

L

2

4.4 Summary and Conclusion

References

Chapter 5: Electron-Counting Rules in Cluster Bonding – Polyhedral Boranes, Elemental Boron, and Boron-Rich Solids

5.1 Introduction

5.2 Wade's Rule

5.3 Localized Bonding Schemes for Bonding in Polyhedral Boranes

5.4 4

n

+2 Interstitial Electron Rule and Ring-Cap Orbital Overlap Compatibility

5.5 Capping Principle

5.6 Electronic Requirement of Condensed Polyhedral Boranes – mno Rule

5.7 Factors Affecting the Stability of Condensed Polyhedral Clusters

5.8 Hypoelectronic Metallaboranes

5.9 Electronic Structure of Elemental Boron and Boron-Rich Metal Borides – Application of Electron-Counting Rules

5.10 Conclusion

References

Chapter 6: Bound Triplet Pairs in the Highest Spin States of Monovalent Metal Clusters

6.1 Introduction

6.2 Can Triplet Pairs Be Bonded?

6.3 Origins of NPFM Bonding in

n

+1

Li

n

Clusters

6.4 Generalization of NPFM Bonding in

n

+1

Li

n

Clusters

6.5 NPFM Bonding in Coinage Metal Clusters

6.6 Valence Bond Modeling of the Bonding in NPFM Clusters of the Coinage Metals

6.7 NPFM Bonding: Resonating Bound Triplet Pairs

6.8 Concluding Remarks: Bound Triplet Pairs

Appendix

6.A Methods and Some Details of Calculations

6.B Symmetry Assignment of the VB Wave Function

6.C The VB Configuration Count and the Expressions for

D

e for NPFM Clusters

References

Chapter 7: Chemical Bonding in Transition Metal Compounds

7.1 Introduction

7.2 Valence Orbitals and Hybridization in Electron-Sharing Bonds of Transition Metals

7.3 Carbonyl Complexes TM(CO)

6

q

(TM

q

= Hf

2−

, Ta

−

, W, Re

+

, Os

2+

, Ir

3+

)

7.4 Phosphane Complexes (CO)

5

TM-PR

3

and N-Heterocyclic Carbene Complexes (CO)

5

TM-NHC (TM = Cr, Mo, W)

7.5 Ethylene and Acetylene Complexes (CO)

5

TM-C

2

H

n

and Cl

4

TM-C

2

H

n

(TM = Cr, Mo, W)

7.6 Group-13 Diyl Complexes (CO)

4

Fe-ER (E = B – Tl; R = Ph, Cp)

7.7 Ferrocene Fe(η

5

-Cp)

2

and Bis(benzene)chromium Cr(η

6

-Bz)

2

7.8 Cluster, Complex, or Electron-Sharing Compound? Chemical Bonding in Mo(EH)

12

and Pd(EH)

8

(E = Zn, Cd, Hg)

7.9 Metal–Metal Multiple Bonding

7.10 Summary

Acknowledgment

References

Chapter 8: Chemical Bonding in Open-Shell Transition-Metal Complexes

8.1 Introduction

8.2 Theoretical Foundations

8.3 Qualitative Interpretation

8.4 Spin Density Distributions—A Case Study

8.5 Summary

Acknowledgments

References

Chapter 9: Modeling Metal–Metal Multiple Bonds with Multireference Quantum Chemical Methods

9.1 Introduction

9.2 Multireference Methods and Effective Bond Orders

9.3 The Multiple Bond in Re

2

Cl

8

2−

9.4 Homonuclear Diatomic Molecules: Cr

2

, Mo

2

, and W

2

9.5 Cr

2

, Mo

2

, and W

2

Containing Complexes

9.6 Fe

2

Complexes

9.7 Concluding Remarks

Acknowledgment

References

Chapter 10: The Quantum Chemistry of Transition Metal Surface Bonding and Reactivity

10.1 Introduction

10.2 The Elementary Quantum-Chemical Model of the Surface Chemical Bond

10.3 Quantum Chemistry of the Surface Chemical Bond

10.4 Metal Particle Composition and Size Dependence

10.5 Lateral Interactions; Reconstruction

10.6 Adsorbate Bond Activation and Formation

10.7 Transition State Analysis: A Summary

References

Chapter 11: Chemical Bonding of Lanthanides and Actinides

11.1 Introduction

11.2 Technical Issues

11.3 The Energy Decomposition Approach to the Bonding in f Block Compounds

11.4 f Block Applications of the Electron Localization Function

11.5 Does Covalency Increase or Decrease across the Actinide Series?

11.6 Multi-configurational Descriptions of Bonding in f Element Complexes

11.7 Concluding Remarks

References

Chapter 12: Direct Estimate of Conjugation, Hyperconjugation, and Aromaticity with the Energy Decomposition Analysis Method

12.1 Introduction

12.2 The EDA Method

12.3 Conjugation

12.4 Hyperconjugation

12.5 Aromaticity

12.6 Concluding Remarks

References

Chapter 13: Magnetic Properties of Aromatic Compounds and Aromatic Transition States

13.1 Introduction

13.2 A Short Historical Review of Aromaticity

13.3 Magnetic Properties of Molecules

13.4 Examples

13.5 Concluding Remarks

References

Chapter 14: Chemical Bonding in Inorganic Aromatic Compounds

14.1 Introduction

14.2 How to Recognize Aromaticity and Antiaromaticity?

14.3 “Conventional” Aromatic/Antiaromatic Inorganic Molecules

14.4 “Unconventional” Aromatic/Antiaromatic Inorganic Molecules

14.5 Summary and Perspectives

Acknowledgments

References

Chapter 15: Chemical Bonding in Solids

15.1 Introduction

15.2 Electronic Structure of Solids: Basic Notions

15.3 Bonding in Solids: Some Illustrative Cases

15.4 Concluding Remarks

Acknowledgments

References

Chapter 16: Dispersion Interaction and Chemical Bonding

16.1 Introduction

16.2 A Short Survey of the Theory of the London Dispersion Energy

16.3 Theoretical Methods to Compute the Dispersion Energy

16.4 Selected Examples

16.5 Conclusion

16.6 Computational Details

References

Chapter 17: Hydrogen Bonding

17.1 Introduction

17.2 Fundamental Properties of Hydrogen Bonds

17.3 Hydrogen Bonds with Varying Strengths

17.4 Hydrogen Bonds in Biological Molecules

17.5 Theoretical Description of Hydrogen Bonding

17.6 Summary

Acknowledgment

References

Chapter 18: Directional Electrostatic Bonding

18.1 Introduction

18.2 Anisotropic Molecular Electrostatic Potential Distribution Around Atoms

18.3 Electrostatic Anisotropy, Donor–Acceptor Interactions and Polarization

18.4 Purely Electrostatic Models

18.5 Difference-Density Techniques

18.6 Directional Noncovalent Interactions

18.7 Conclusions

Acknowledgments

References

Index

End User License Agreement

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Guide

Cover

Table of Contents

Preface

Chapter 1: Chemical Bonding of Main-Group Elements

List of Illustrations

Figure 1.1

Figure 1.2

Figure 1.3

Scheme 2.1

Figure 2.1

Figure 2.2

Figure 2.3

Figure 2.4

Figure 2.5

Figure 2.6

Figure 2.7

Figure 3.1

Figure 3.2

Figure 3.3

Figure 3.4

Figure 3.5

Figure 3.6

Figure 3.7

Figure 3.8

Figure 4.1

Figure 4.2

Figure 4.3

Figure 4.4

Figure 4.5

Figure 4.6

Figure 4.7

Figure 4.8

Figure 4.9

Figure 4.10

Figure 4.11

Figure 4.12

Figure 4.13

Figure 4.14

Figure 4.15

Figure 4.16

Figure 4.17

Figure 4.18

Figure 4.19

Figure 4.20

Figure 4.21

Figure 4.22

Figure 4.23

Figure 4.24

Figure 5.1

Figure 5.2

Figure 5.3

Figure 5.4

Figure 5.5

Figure 5.6

Figure 5.7

Figure 5.8

Figure 5.9

Figure 5.10

Figure 5.11

Figure 5.12

Figure 5.13

Figure 5.14

Figure 5.15

Figure 5.16

Figure 5.17

Figure 5.18

Figure 5.19

Figure 5.20

Figure 5.21

Figure 5.22

Figure 5.23

Figure 5.24

Figure 5.25

Figure 5.26

Figure 5.27

Figure 5.28

Figure 5.29

Figure 5.30

Figure 5.31

Figure 5.32

Figure 5.33

Figure 5.34

Figure 5.35

Figure 5.36

Figure 6.1

Figure 6.2

Figure 6.3

Figure 6.4

Figure 6.5

Figure 6.6

Figure 6.7

Figure 6.8

Scheme 6.1

Figure 6.9

Figure 6.10

Figure 6.11

Figure 6.12

Figure 6.13

Figure 6.14

Figure 6.15

Figure 7.1

Figure 7.2

Figure 7.3

Figure 7.4

Figure 7.5

Figure 7.6

Figure 7.7

Figure 7.8

Figure 7.9

Figure 7.10

Figure 7.11

Figure 7.12

Figure 7.13

Figure 7.14

Figure 7.15

Figure 7.16

Figure 7.17

Figure 7.18

Figure 7.19

Figure 7.20

Figure 8.1

Figure 8.2

Figure 8.3

Figure 8.4

Figure 9.1

Figure 9.2

Figure 9.3

Figure 9.4

Figure 10.1

Figure 10.2

Figure 10.3

Figure 10.4

Figure 10.5

Figure 10.6

Figure 10.7

Figure 10.8

Figure 10.10

Figure 10.9

Figure 10.11

Figure 10.12

Figure 10.13

Figure 10.14

Figure 10.15

Figure 10.16

Figure 10.17

Figure 10.18

Figure 10.19

Figure 10.20

Figure 10.21

Figure 10.22

Figure 10.23

Figure 10.24

Figure 10.25

Figure 10.26

Figure 10.27

Figure 10.28

Figure 10.29

Figure 10.30

Figure 10.31

Figure 10.32

Figure 10.33

Figure 10.34

Figure 10.35

Figure 10.36

Figure 10.37

Figure 10.38

Scheme 11.1

Figure 11.1

Figure 11.2

Figure 11.3

Figure 11.4

Figure 11.5

Figure 11.6

Figure 11.7

Figure 11.8

Figure 11.9

Figure 11.10

Figure 12.1

Scheme 12.1

Figure 12.2

Figure 12.3

Figure 12.4

Figure 12.5

Figure 12.6

Figure 12.7

Figure 12.8

Figure 12.9

Figure 12.10

Figure 12.11

Figure 12.12

Figure 13.1

Figure 13.2

Figure 13.3

Figure 13.4

Figure 13.5

Figure 13.6

Figure 13.7

Figure 13.8

Figure 13.9

Figure 13.10

Figure 13.11

Figure 13.12

Figure 13.13

Figure 13.14

Figure 13.15

Figure 13.16

Figure 13.17

Figure 13.18

Figure 13.19

Figure 13.20

Figure 13.21

Figure 13.22

Figure 13.23

Figure 13.24

Figure 13.25

Figure 13.26

Figure 13.27

Figure 13.28

Figure 14.1

Figure 14.2

Figure 14.3

Figure 14.4

Figure 14.5

Figure 14.6

Figure 14.7

Figure 14.8

Figure 14.9

Figure 14.10

Figure 15.1

Figure 15.2

Figure 15.3

Figure 15.4

Figure 15.5

Figure 15.6

Figure 15.7

Figure 15.8

Figure 15.9

Figure 15.10

Figure 15.11

Figure 15.12

Figure 15.13

Figure 15.14

Figure 15.15

Figure 15.16

Figure 15.17

Figure 15.18

Figure 16.1

Figure 16.2

Figure 16.3

Figure 16.4

Figure 16.5

Figure 16.6

Figure 16.7

Figure 16.8

Figure 16.9

Figure 16.10

Figure 16.11

Figure 17.1

Figure 17.2

Figure 17.3

Figure 17.4

Figure 17.5

Scheme 17.1

Figure 17.6

Figure 17.7

Figure 17.8

Scheme 17.2

Figure 17.9

Scheme 17.3

Scheme 17.4

Figure 18.1

Figure 18.2

Figure 18.3

Figure 18.4

Figure 18.5

Figure 18.6

List of Tables

Table 1.1

Table 2.1

Table 2.2

Table 2.3

Table 2.4

Table 4.1

Table 4.2

Table 4.3

Table 4.4

Table 4.5

Table 4.6

Table 4.7

Table 4.8

Table 4.9

Table 5.1

Table 7.1

Table 7.2

Table 7.3

Table 7.4

Table 7.5

Table 7.6

Table 7.7

Table 7.8

Table 7.9

Table 7.10

Table 7.11

Table 7.12

Table 7.13

Table 7.14

Table 9.1

Table 9.2

Table 10.1

Table 10.2

Table 10.3

Table 10.4

Table 10.5

Table 10.6

Table 10.7

Table 11.1

Table 11.2

Table 11.3

Table 12.1

Table 12.2

Table 12.3

Table 12.4

Table 12.5

Table 12.6

Table 12.7

Table 13.1

Table 13.2

Table 14.1

Table 17.1

Table 17.2

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Edited by Gernot Frenking and Sason Shaik

The Chemical Bond

Chemical Bonding Across the Periodic Table

Editors

Prof. Dr. Gernot Frenking

Philipps-Universität Marburg

FB Chemie

Hans-Meerwein-Strasse

35032 Marburg

Germany

Prof. Dr. Sason Shaik

Hebrew University

Institut of Chemistry

Givat Ram Campus

91904 Jerusalem

Israel

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Preface

The chemical bond is the backbone of chemistry. It defines chemistry as the science of understanding and transformation of the physical world in terms of interatomic interactions, which are considered as chemical bonds. Thus, chemistry appears right at the beginning as a fuzzy discipline because the distinction between chemical and nonchemical interatomic interactions is not exactly defined, which creates ongoing controversial debates. But the fuzziness of chemical bonding posed no obstacle for the advancement of chemical research from an esoteric playground to a highly sophisticated academic discipline, which became the basis for industrial growth and economic wealth. In the absence of a physical understanding of chemical bonding, chemists used their imagination and creativity for designing models that proved to be very useful for rationalizing experimental observations.

The development of chemical bonding models, which is an integral part of the progress in experimental chemistry, is a fascinating chapter in the history of mankind. It goes beyond the mere realm of natural science and is part of the evolution of human culture. Chemists analyzed and synthesized in the past centuries a steadily increasing number of new compounds, which required a systematic ordering system to become comprehensible. In order to understand the enormous diversity of molecules and solids, which constitute the chemical universe, chemists developed bonding models that served two purposes. One purpose was to provide an understanding for the observed species, which were classified according to well-defined rules. The second purpose was to establish a guideline for new experiments; a goal that needed a scientific hypothesis in order to distinguish research from random activity.