The chemical bond : chemical bonding across the perodic table / edited by Gernot Frenking and Sason Shaik.

Format:

Book

Contributor:

Frenking, G. (Gernot), editor.

Shaik, Sason, editor.

Language:

English

Subjects (All):

Chemical bonds--Mathematical models.

Chemical bonds.

Chemical bonds--Congresses.

Physical Description:

1 online resource (544 p.)

Edition:

1st ed.

Place of Publication:

Weinheim, Germany : Wiley-VCH Verlag GmbH & Co, 2014.

Language Note:

English

Summary:

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.

Contents:

Intro

The Chemical Bond

Contents

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

1.2.1 High Electronegativity and Small Size of the 2p-Elements

1.2.1.1 Hybridization Defects

1.2.2 The Inert-Pair Effect and its Dependence on Partial Charge of the Central Atom

1.2.3 Stereo-Chemically Active versus Inactive Lone Pairs

1.2.4 The Multiple-Bond Paradigm and the Question of Bond Strengths

1.2.5 Influence of Hybridization Defects on Magnetic-Resonance Parameters

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 E2 (E = N - Bi)

2.3 Comparative Bonding Analysis of N2 and P2 with N4 and P4

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

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 SF2 and OF2 (and Beyond)

3.4.1 SF2(X1A1)

3.4.2 SF2(a3B1)

3.4.3 SF2(b3A2)

3.4.4 OF2(X1A1)

3.4.5 Triplet states of OF2

3.4.6 SF3 and SF4

3.4.7 SF5 and SF6

3.5 Comparison to Other Models

3.5.1 Rundle-Pimentel 3c-4e Model.

3.5.2 Diabatic States Model

3.5.3 Democracy Principle

3.6 Concluding Remarks

Chapter 4 Donor-Acceptor Complexes of Main-Group Elements

4.1 Introduction

4.2 Single-Center Complexes EL2

4.2.1 Carbones CL2

4.2.2 Isoelectronic Group 15 and Group 13 Homologues (N+)L2 and (BH)L2

4.2.3 Donor-Acceptor Bonding in Heavier Tetrylenes ER2 and Tetrylones EL2 (E = Si - Pb)

4.3 Two-Center Complexes E2L2

4.3.1 Two-Center Group 14 Complexes Si2L2 - Pb2L2 (L = NHC)

4.3.2 Two-Center Group 13 and Group 15 Complexes B2L2 and N2L2

4.4 Summary and Conclusion

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 4n+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

5.7.1 Exo-polyhedral Interactions

5.7.2 Orbital Compatibility

5.8 Hypoelectronic Metallaboranes

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

5.9.1 α-Rhombohedral Boron

5.9.2 β-Rhombohedral Boron

5.9.3 Alkali Metal-Indium Clusters

5.9.4 Electronic Structure of Mg~5B44

5.10 Conclusion

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

6.1 Introduction

6.2 Can Triplet Pairs Be Bonded?

6.2.1 A Prototypical Bound Triplet Pair in 3Li2

6.2.2 The NPFM Bonded Series of n+1Li_n (n=2-10)

6.3 Origins of NPFM Bonding in n+1Li_n Clusters

6.3.1 Orbital Cartoons for the NPFM Bonding of the 3Σu+ State of Li2.

6.4 Generalization of NPFM Bonding in n+1Li_n Clusters

6.4.1 VB Mixing Diagram Representation of the Bonding in 3Li_2

6.4.2 VB Modeling of n+1Li_n Patterns

6.5 NPFM Bonding in Coinage Metal Clusters

6.5.1 Structures and Bonding of Coinage Metal NPFM 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 De for NPFM Clusters

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)6q (TMq = Hf2-, Ta-, W, Re+, Os2+, Ir3+)

7.4 Phosphane Complexes (CO)5TM-PR3 and N-Heterocyclic Carbene Complexes (CO)5TM-NHC (TM = Cr, Mo, W)

7.5 Ethylene and Acetylene Complexes (CO)5TM-C2Hn and Cl4TM-C2Hn (TM = Cr, Mo, W)

7.6 Group-13 Diyl Complexes (CO)4Fe-ER (E = B - Tl

R = Ph, Cp)

7.7 Ferrocene Fe(η5-Cp)2 and Bis(benzene)chromium Cr(η6-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

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

8.1 Introduction

8.2 Theoretical Foundations

8.2.1 Definition of Open-Shell Electronic Structures

8.2.2 The Configuration Interaction Ansatz

8.2.2.1 The Truncation Procedure

8.2.2.2 Density Matrices

8.2.3 Ab Initio Single-Reference Approaches

8.2.4 Ab Initio Multireference Approaches

8.2.5 Density Functional Theory for Open-Shell Molecules.

8.3 Qualitative Interpretation

8.3.1 Local Spin

8.3.2 Broken Spin Symmetry

8.3.3 Analysis of Bond Orders

8.3.4 Atoms in Molecules

8.3.5 Entanglement Measures for Single- and Multireference Correlation Effects

8.4 Spin Density Distributions-A Case Study

8.4.1 A One-Determinant Picture

8.4.2 A Multiconfigurational Study

8.5 Summary

Acknowledgments

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 Re2Cl82-

9.4 Homonuclear Diatomic Molecules: Cr2, Mo2, and W2

9.5 Cr2, Mo2, and W2 Containing Complexes

9.6 Fe2 Complexes

9.7 Concluding Remarks

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

10.3.1 Adatom Adsorption Energy Dependence on Coordinative Unsaturation of Surface Atoms

10.3.2 Adatom Adsorption Energy as a Function of Metal Position in the Periodic System

10.3.3 Molecular Adsorption

Adsorption of CO

10.3.4 Surface Group Orbitals

10.3.5 Adsorbate Coordination in Relation to Adsorbate Valence

10.4 Metal Particle Composition and Size Dependence

10.4.1 Alloying: Coordinative Unsaturation versus Increased Overlap Energies

10.4.2 Particle Size Dependence

10.5 Lateral Interactions

Reconstruction

10.6 Adsorbate Bond Activation and Formation

10.6.1 The Reactivity of Different Metal Surfaces

10.6.2 The Quantum-Chemical View of Bond Activation

10.6.2.1 Activation of the Molecular π Bond (Particle Shape Dependence)

10.6.2.2 The Uniqueness of the (100) Surface.

10.6.2.3 Activation of the Molecular σ Bond

CH4 and NH3

10.7 Transition State Analysis: A Summary

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

11.3.1 A Comparison of U-N and U-O Bonding in Uranyl(VI) Complexes

11.3.2 Toward a 32-Electron Rule

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

11.6.1 U2: A Quintuply Bonded Actinide Dimer

11.6.2 Bonding in the Actinyls

11.6.3 Oxidation State Ambiguity in the f Block Metallocenes

11.7 Concluding Remarks

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

12.3.1 Conjugation in 1,3-Butadienes, 1,3-Butadiyne, Polyenes, and Enones

12.3.2 Correlation with Experimental Data

12.4 Hyperconjugation

12.4.1 Hyperconjugation in Ethane and Ethane-Like Compounds

12.4.2 Group 14 β-Effect

12.5 Aromaticity

12.5.1 Aromaticity in Neutral Exocyclic Substituted Cyclopropenes (HC)2C = X

12.5.2 Aromaticity in Group 14 Homologs of the Cyclopropenylium Cation

12.5.3 Aromaticity in Metallabenzenes

12.6 Concluding Remarks

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

13.3.1 Exaltation and Anisotropy of Magnetic Susceptibility

13.3.2 Chemical Shifts in NMR

13.3.3 Quantum Theoretical Treatment

13.4 Examples

13.4.1 Benzene and Borazine.

13.4.2 Pyridine, Phosphabenzene, and Silabenzene.

Notes:

Bibliographic Level Mode of Issuance: Monograph

Includes bibliographical references at the end of each chapters and index.

Description based on online resource; title from PDF title page (ebrary, viewed May 31, 2014).

ISBN:

9783527664672

352766467X

9783527664658

3527664653

9783527664689

3527664688

OCLC:

882264527