The Chemical Bond

Preface

CHEMICAL BONDING OF MAIN-GROUP ELEMENTS
Introduction and Definitions
The Lack of Radial Nodes of the 2p Shell Accounts for Most of the Peculiarities of the Chemistry of the 2p-Elements
The Role of the Outer d-Orbitals in Bonding
Secondary Periodicities: Incomplete-Screening and Relativistic Effects
"Honorary d-Elements": the Peculiarities of Structure and Bonding of the Heavy Group 2 Elements
Concluding Remarks

MULTIPLE BONDING OF HEAVY MAIN-GROUP ATOMS
Introduction
Bonding Analysis of Diatomic Molecules E2 (E = N - Bi)
Comparative Bonding Analysis of N2 and P2 with N4 and P4
Bonding Analysis of the Tetrylynes HEEH (E = C - Pb)
Explaining the Different Structures of the Tetrylynes HEEH (E = C - Pb)
Energy Decomposition Analysis of the Tetrylynes HEEH (E = C - Pb)
Conclusion

THE ROLE OF RECOUPLED PAIR BONDING IN HYPERVALENT MOLECULES
Introduction
Multireference Wavefunction Treatment of Bonding
Low-Lying States of SF and OF
Low-Lying States of SF2 and OF2 (and Beyond)
Comparison to Other Models
Concluding Remarks

DONOR-ACCEPTOR COMPLEXES OF MAIN-GROUP ELEMENTS
Introduction
Single-Center Complexes EL2
Two-Center Complexes E2L2
Summary and Conclusion

ELECTRON-COUNTING RULES IN CLUSTER BONDING - POLYHEDRAL BORANES, ELEMENTAL BORON, AND BORON-RICH SOLIDS
Introduction
Wade's Rule
Localized Bonding Schemes for Bonding in Polyhedral Boranes
4n + 2 Interstitial Electron Rule and Ring-Cap Orbital Overlap Compatibility
Capping Principle
Electronic Requirement of Condensed Polyhedral Boranes - mno Rule
Factors Affecting the Stability of Condensed Polyhedral Clusters
Hypoelectronic Metallaboranes
Electronic Structure of Elemental Boron and Boron-Rich Metal Borides - Application of Electron-Counting Rules
Conclusion

BOUND TRIPLET PAIRS IN THE HIGHEST SPIN STATES OF MONOVALENT METAL CLUSTERS
Introduction
Can Triplet Pairs Be Bonded?
Origins of NPFM Bonding in n+1Lin Clusters
Generalization of NPFM Bonding in n+1Lin Clusters
NPFM Bonding in Coinage Metal Clusters
Valence Bond Modeling of the Bonding in NPFM Clusters of the Coinage Metals
NPFM Bonding: Resonating Bound Triplet Pairs
Concluding Remarks: Bound Triplet Pairs
Appendix

CHEMICAL BONDING IN TRANSITION METAL COMPOUNDS
Introduction
Valence Orbitals and Hybridization in Electron-Sharing Bonds of Transition Metals
Carbonyl Complexes TM(CO)6q (TMq = Hf2-, Ta-, W, Re+, Os2+, Ir3+)
Phosphane Complexes (CO)5TM-PR3 and N-Heterocyclic Carbene Complexes (CO)5TM-NHC (TM = Cr, Mo, W)
Ethylene and Acetylene Complexes (CO)5TM-C2Hn and Cl4TM-C2Hn (TM = Cr, Mo, W)
Group-13 Diyl Complexes (CO)4Fe-ER ( E = B - Tl; R = Ph, Cp)
Ferrocene Fe(n5-Cp)2 and Bis(benzene)chromium Cr(n6-Bz)2
Cluster, Complex, or Electron-Sharing Compound? Chemical Bonding in Mo(Eh)12 and Pd(EH)8 (E = Zn, Cd, Hg)
Metal-Metal Multiple Bonding
Summary

CHEMICAL BONDING IN OPEN-SHELL TRANSITION-METAL COMPLEXES
Introduction
Theoretical Foundations
Qualitative Interpretation
Spin Density Distributions - A Case Study
Summary

MODELING METAL-METAL MULTIPLE BONDS WITH MULTIREFERENCE QUANTUM CHEMICAL METHODS
Introduction
Multireferance Methods and Effective Bond Orders
The Multiple Bond in Re2Cl8 2-
Homonuclear Diatomic Molecules: Cr2, Mo2, and W2
Cr2, Mo2, and W2 Containing Complexes
Fe2 Complexes
Concluding Remarks

THE QUANTUM CHEMISTRY OF TRANSITION METAL SURFACE BONDING AND REACTIVITY
Introduction
The Elementary Quantum-Chemical Model of the Surface Chemical Bond
Quantum Chemistry of the Surface Chemical Bond
Metal Particle Composition and Size Dependence
Lateral Interactions; Reconstruction
Adsorbate Bond Activation and Formation
Transition State Analysis: A Summary

CHEMICAL BONDING OF LANTHANIDES AND ACTINIDES
Introduction
Technical Issues
The Energy Decomposition Approach to the Bonding in f Block Compounds
f Block Applications of the Electron Localization Function
Does Covalency Increase or Decrease across the Actinide Series?
Multi-configurational Descriptions of Bonding in f Element Complexes
Concluding Remark