The Chemical Bond: Chemical Bonding Across the Periodic Table

The Chemical Bond: Chemical Bonding Across the Periodic Table

By: Gernot Frenking (editor), Sason Shaik (editor)Hardback

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Description

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.

About Author

Gernot Frenking studied chemistry at the Technical University Aachen (Germany). He then became a research atudent in the group of Prof. Kenichi Fukui in Kyoto (Japan) and completed his PhD and his habilitation at Technical University Berlin (Germany). He was then a visiting scientist at the University of California, Berkeley (USA) and a staff scientist at SRI International in Menlo Park, California (USA). Since 1990 he is Professor for Computational Chemistry at the Philipps-Universitat Marburg. Sason Shaik is a graduate of the University of Washington (USA), where he also obtained his PhD. After a postdoctoral year at Cornell University, he became Lecturer at Ben-Gurion University of the Negev (Israel), where he became Professor in 1988. In 1992 he moved to The Hebrew University where he is Professor and the Director of the Lise Meitner-Minerva Center for Computational Quantum Chemistry.

Contents

Preface XV List of Contributors XIX 1 Chemical Bonding of Main-Group Elements 1 Martin Kaupp 1.1 Introduction and Definitions 1 1.2 The Lack of Radial Nodes of the 2p Shell Accounts for Most of the Peculiarities of the Chemistry of the 2p-Elements 2 1.2.1 High Electronegativity and Small Size of the 2p-Elements 4 1.2.1.1 Hybridization Defects 4 1.2.2 The Inert-Pair Effect and its Dependence on Partial Charge of the Central Atom 7 1.2.3 Stereo-Chemically Active versus Inactive Lone Pairs 10 1.2.4 TheMultiple-Bond Paradigm and the Question of Bond Strengths 13 1.2.5 Influence of Hybridization Defects on Magnetic-Resonance Parameters 14 1.3 The Role of the Outer d-Orbitals in Bonding 15 1.4 Secondary Periodicities: Incomplete-Screening and Relativistic Effects 17 1.5 Honorary d-Elements : the Peculiarities of Structure and Bonding of the Heavy Group 2 Elements 19 1.6 Concluding Remarks 21 References 21 2 Multiple Bonding of Heavy Main-Group Atoms 25 Gernot Frenking 2.1 Introduction 25 2.2 Bonding Analysis of Diatomic Molecules E2 (E=N Bi) 27 2.3 Comparative Bonding Analysis of N2 and P2 with N4 and P4 29 2.4 Bonding Analysis of the Tetrylynes HEEH (E=C Pb) 32 2.5 Explaining the Different Structures of the Tetrylynes HEEH (E=C Pb) 34 2.6 Energy Decomposition Analysis of the Tetrylynes HEEH (E=C Pb) 41 2.7 Conclusion 46 Acknowledgment 47 References 47 3 The Role of Recoupled Pair Bonding in Hypervalent Molecules 49 David E. Woon and Thom H. Dunning Jr. 3.1 Introduction 49 3.2 Multireference Wavefunction Treatment of Bonding 50 3.3 Low-Lying States of SF and OF 53 3.4 Low-Lying States of SF2 and OF2 (and Beyond) 58 3.4.1 SF2(X1A1) 58 3.4.2 SF2(a3B1) 59 3.4.3 SF2(b3A2) 61 3.4.4 OF2(X1A1) 62 3.4.5 Triplet states of OF2 62 3.4.6 SF3 and SF4 63 3.4.7 SF5 and SF6 64 3.5 Comparison to Other Models 64 3.5.1 Rundle Pimentel 3c-4e Model 64 3.5.2 Diabatic States Model 66 3.5.3 Democracy Principle 67 3.6 Concluding Remarks 67 References 68 4 Donor Acceptor Complexes of Main-Group Elements 71 Gernot Frenking and Ralf Tonner 4.1 Introduction 71 4.2 Single-Center Complexes EL2 73 4.2.1 Carbones CL2 73 4.2.2 Isoelectronic Group 15 and Group 13 Homologues (N+)L2 and (BH)L2 82 4.2.3 Donor Acceptor Bonding in Heavier Tetrylenes ER2 and Tetrylones EL2 (E=Si Pb) 88 4.3 Two-Center Complexes E2L2 94 4.3.1 Two-Center Group 14 Complexes Si2L2 Pb2L2 (L=NHC) 95 4.3.2 Two-Center Group 13 and Group 15 Complexes B2L2 and N2L2 101 4.4 Summary and Conclusion 110 References 110 5 Electron-Counting Rules in Cluster Bonding Polyhedral Boranes, Elemental Boron, and Boron-Rich Solids 113 Chakkingal P. Priyakumari and Eluvathingal D. Jemmis 5.1 Introduction 113 5.2 Wade s Rule 114 5.3 Localized Bonding Schemes for Bonding in Polyhedral Boranes 119 5.4 4n + 2 Interstitial Electron Rule and Ring-Cap Orbital Overlap Compatibility 122 5.5 Capping Principle 125 5.6 Electronic Requirement of Condensed Polyhedral Boranes mno Rule 126 5.7 Factors Affecting the Stability of Condensed Polyhedral Clusters 134 5.7.1 Exo-polyhedral Interactions 134 5.7.2 Orbital Compatibility 135 5.8 Hypoelectronic Metallaboranes 136 5.9 Electronic Structure of Elemental Boron and Boron-Rich Metal Borides Application of Electron-Counting Rules 139 5.9.1 -Rhombohedral Boron 139 5.9.2 -Rhombohedral Boron 140 5.9.3 Alkali Metal-Indium Clusters 142 5.9.4 Electronic Structure of Mg 5B44 143 5.10 Conclusion 144 References 145 6 Bound Triplet Pairs in the Highest Spin States of Monovalent Metal Clusters 149 David Danovich and Sason Shaik 6.1 Introduction 149 6.2 Can Triplet Pairs Be Bonded? 150 6.2.1 A Prototypical Bound Triplet Pair in 3Li2 150 6.2.2 The NPFM Bonded Series of n+1Lin (n = 2 10) 152 6.3 Origins of NPFM Bonding in n+1Lin Clusters 152 6.3.1 Orbital Cartoons for the NPFM Bonding of the 3 +u State of Li2 154 6.4 Generalization of NPFM Bonding in n+1Lin Clusters 156 6.4.1 VB Mixing Diagram Representation of the Bonding in 3Li2 156 6.4.2 VB Modeling of n+1Lin Patterns 158 6.5 NPFM Bonding in Coinage Metal Clusters 161 6.5.1 Structures and Bonding of Coinage Metal NPFM Clusters 161 6.6 Valence Bond Modeling of the Bonding in NPFM Clusters of the Coinage Metals 163 6.7 NPFM Bonding: Resonating Bound Triplet Pairs 167 6.8 Concluding Remarks: Bound Triplet Pairs 168 Appendix 170 6.A Methods and Some Details of Calculations 170 6.B Symmetry Assignment of the VB Wave Function 170 6.C The VB Configuration Count and the Expressions for De for NPFM Clusters 171 References 172 7 Chemical Bonding in Transition Metal Compounds 175 Gernot Frenking 7.1 Introduction 175 7.2 Valence Orbitals and Hybridization in Electron-Sharing Bonds of Transition Metals 177 7.3 Carbonyl Complexes TM(CO) q 6 (TMq =Hf2 , Ta , W, Re+, Os2+, Ir3+) 181 7.4 Phosphane Complexes (CO)5TM-PR3 and N-Heterocyclic Carbene Complexes (CO)5TM-NHC (TM=Cr, Mo, W) 187 7.5 Ethylene and Acetylene Complexes (CO)5TM-C2Hn and Cl4TM-C2Hn (TM=Cr, Mo, W) 190 7.6 Group-13 Diyl Complexes (CO)4Fe-ER (E=B Tl; R=Ph, Cp) 195 7.7 Ferrocene Fe( 5-Cp)2 and Bis(benzene)chromium Cr( 6-Bz)2 199 7.8 Cluster, Complex, or Electron-Sharing Compound? Chemical Bonding in Mo(EH)12 and Pd(EH)8 (E=Zn, Cd, Hg) 203 7.9 Metal Metal Multiple Bonding 211 7.10 Summary 214 Acknowledgment 214 References 214 8 Chemical Bonding in Open-Shell Transition-Metal Complexes 219 Katharina Boguslawski and Markus Reiher 8.1 Introduction 219 8.2 Theoretical Foundations 220 8.2.1 Definition of Open-Shell Electronic Structures 221 8.2.2 The Configuration Interaction Ansatz 222 8.2.2.1 The Truncation Procedure 222 8.2.2.2 Density Matrices 222 8.2.3 Ab Initio Single-Reference Approaches 223 8.2.4 Ab Initio Multireference Approaches 224 8.2.5 Density Functional Theory for Open-Shell Molecules 229 8.3 Qualitative Interpretation 230 8.3.1 Local Spin 230 8.3.2 Broken Spin Symmetry 233 8.3.3 Analysis of Bond Orders 235 8.3.4 Atoms in Molecules 237 8.3.5 Entanglement Measures for Single- and Multireference Correlation Effects 239 8.4 Spin Density Distributions A Case Study 243 8.4.1 A One-Determinant Picture 243 8.4.2 A Multiconfigurational Study 245 8.5 Summary 246 Acknowledgments 247 References 247 9 Modeling Metal Metal Multiple Bonds with Multireference Quantum Chemical Methods 253 Laura Gagliardi 9.1 Introduction 253 9.2 Multireference Methods and Effective Bond Orders 253 9.3 The Multiple Bond in Re2Cl 2 8 254 9.4 Homonuclear Diatomic Molecules: Cr2, Mo2, andW2 255 9.5 Cr2, Mo2, andW2 Containing Complexes 259 9.6 Fe2 Complexes 264 9.7 Concluding Remarks 265 Acknowledgment 266 References 266 10 The Quantum Chemistry of Transition Metal Surface Bonding and Reactivity 269 Rutger A. van Santen and Ivo A. W. Filot 10.1 Introduction 269 10.2 The Elementary Quantum-Chemical Model of the Surface Chemical Bond 272 10.3 Quantum Chemistry of the Surface Chemical Bond 276 10.3.1 Adatom Adsorption Energy Dependence on Coordinative Unsaturation of Surface Atoms 276 10.3.2 Adatom Adsorption Energy as a Function of Metal Position in the Periodic System 284 10.3.3 Molecular Adsorption; Adsorption of CO 286 10.3.4 Surface Group Orbitals 296 10.3.5 Adsorbate Coordination in Relation to Adsorbate Valence 301 10.4 Metal Particle Composition and Size Dependence 303 10.4.1 Alloying: Coordinative Unsaturation versus Increased Overlap Energies 303 10.4.2 Particle Size Dependence 305 10.5 Lateral Interactions; Reconstruction 310 10.6 Adsorbate Bond Activation and Formation 317 10.6.1 The Reactivity of Different Metal Surfaces 317 10.6.2 The Quantum-Chemical View of Bond Activation 321 10.6.2.1 Activation of the Molecular Bond (Particle Shape Dependence) 321 10.6.2.2 The Uniqueness of the (100) Surface 323 10.6.2.3 Activation of the Molecular Bond; CH4 and NH3 325 10.7 Transition State Analysis: A Summary 328 References 333 11 Chemical Bonding of Lanthanides and Actinides 337 Nikolas Kaltsoyannis and Andrew Kerridge 11.1 Introduction 337 11.2 Technical Issues 338 11.3 The Energy Decomposition Approach to the Bonding in f Block Compounds 338 11.3.1 A Comparison of U N and U O Bonding in Uranyl(VI) Complexes 339 11.3.2 Toward a 32-Electron Rule 340 11.4 f Block Applications of the Electron Localization Function 341 11.5 Does Covalency Increase or Decrease across the Actinide Series? 342 11.6 Multi-configurational Descriptions of Bonding in f Element Complexes 347 11.6.1 U2: A Quintuply Bonded Actinide Dimer 347 11.6.2 Bonding in the Actinyls 349 11.6.3 Oxidation State Ambiguity in the f Block Metallocenes 350 11.7 Concluding Remarks 353 References 354 12 Direct Estimate of Conjugation, Hyperconjugation, and Aromaticity with the Energy Decomposition Analysis Method 357 Israel Fern'andez 12.1 Introduction 357 12.2 The EDA Method 359 12.3 Conjugation 361 12.3.1 Conjugation in 1,3-Butadienes, 1,3-Butadiyne, Polyenes, and Enones 361 12.3.2 Correlation with Experimental Data 363 12.4 Hyperconjugation 370 12.4.1 Hyperconjugation in Ethane and Ethane-Like Compounds 370 12.4.2 Group 14 -Effect 371 12.5 Aromaticity 372 12.5.1 Aromaticity in Neutral Exocyclic Substituted Cyclopropenes (HC)2C=X 374 12.5.2 Aromaticity in Group 14 Homologs of the Cyclopropenylium Cation 375 12.5.3 Aromaticity in Metallabenzenes 376 12.6 Concluding Remarks 378 References 379 13 Magnetic Properties of Aromatic Compounds and Aromatic Transition States 383 Rainer Herges 13.1 Introduction 383 13.2 A Short Historical Review of Aromaticity 384 13.3 Magnetic Properties of Molecules 386 13.3.1 Exaltation and Anisotropy of Magnetic Susceptibility 387 13.3.2 Chemical Shifts in NMR 391 13.3.3 Quantum Theoretical Treatment 392 13.4 Examples 397 13.4.1 Benzene and Borazine 397 13.4.2 Pyridine, Phosphabenzene, and Silabenzene 398 13.4.3 Fullerenes 400 13.4.4 Huckel and Mobius Structures 401 13.4.5 Homoaromatic Molecules 403 13.4.6 Organometallic Compounds 404 13.4.7 Aromatic Transition States 406 13.4.8 Coarctate Transition States 411 13.5 Concluding Remarks 415 References 415 14 Chemical Bonding in Inorganic Aromatic Compounds 421 Ivan A. Popov and Alexander I. Boldyrev 14.1 Introduction 421 14.2 How to Recognize Aromaticity and Antiaromaticity? 422 14.3 Conventional Aromatic/Antiaromatic Inorganic Molecules 426 14.3.1 Inorganic B3N3H6 Borazine and 1,3,2,4-Diazadiboretiidine B2N2H4 427 14.3.2 Aromatic P 2 4 , P 5 , P6 and Their Analogs 428 14.4 Unconventional Aromatic/Antiaromatic Inorganic Molecules 430 14.4.1 -Aromatic and -Antiaromatic Species 431 14.4.2 -/ -Aromatic, -/ -Antiaromatic, and Species with -/ -Conflicting Aromaticity 432 14.4.3 -/ -/ -Aromatic, -/ -/ -Antiaromatic, and Species with -/ -/ -Conflicting Aromaticity 436 14.5 Summary and Perspectives 440 Acknowledgments 441 References 441 15 Chemical Bonding in Solids 445 Pere Alemany and Enric Canadell 15.1 Introduction 445 15.2 Electronic Structure of Solids: Basic Notions 447 15.2.1 Bloch Orbitals, Crystal Orbitals, and Band Structure 447 15.2.2 Fermi Level and Electron Counting 449 15.2.3 Peierls Distortions 451 15.2.4 Density of States and its Analysis 453 15.2.5 Electronic Localization 456 15.3 Bonding in Solids: Some Illustrative Cases 458 15.3.1 Covalent Bonds in Polar Metallic Solids: A3Bi2 and A4Bi5 (A=K, Rb, Cs) 459 15.3.2 Electronic Localization: Magnetic versus Metallic Behavior in K4P3 462 15.3.3 Crystal versus Electronic Structure: Are There Really Polyacetylene-Like Gallium Chains in Li2Ga? 466 15.3.4 Ba7Ga4Sb9: Do the Different Cations in Metallic Zintl Phases Play the Same Role? 470 15.4 Concluding Remarks 473 Acknowledgments 474 References 474 16 Dispersion Interaction and Chemical Bonding 477 Stefan Grimme 16.1 Introduction 477 16.2 A Short Survey of the Theory of the London Dispersion Energy 480 16.3 Theoretical Methods to Compute the Dispersion Energy 485 16.3.1 General 486 16.3.2 Supermolecular Wave Function Theory (WFT) 486 16.3.3 Supermolecular Density Functional Theory (DFT) 488 16.3.4 Symmetry-Adapted Perturbation Theory (SAPT) 490 16.4 Selected Examples 492 16.4.1 Substituted Ethenes 492 16.4.2 Steric Crowding Can Stabilize a Labile Molecule: Hexamethylethane Derivatives 493 16.4.3 Overcoming Coulomb Repulsion in a Transition Metal Complex 494 16.5 Conclusion 495 16.6 Computational Details 496 References 496 17 Hydrogen Bonding 501 Hajime Hirao and Xiaoqing Wang 17.1 Introduction 501 17.2 Fundamental Properties of Hydrogen Bonds 502 17.3 Hydrogen Bonds with Varying Strengths 504 17.4 Hydrogen Bonds in Biological Molecules 506 17.5 Theoretical Description of Hydrogen Bonding 508 17.5.1 Valence Bond Description of the Hydrogen Bond 508 17.5.2 Electrostatic and Orbital Interactions in H Bonds 509 17.5.3 Ab Initio and Density Functional Theory Calculations of Water Dimer 510 17.5.4 Energy Decomposition Analysis 511 17.5.5 Electron Density Distribution Analysis 513 17.5.6 Topological Analysis of the Electron Density and the Electron Localization Function 514 17.5.7 Resonance-Assisted Hydrogen Bonding 515 17.5.8 Improper, Blueshifting Hydrogen Bonds 516 17.6 Summary 517 Acknowledgment 517 References 517 18 Directional Electrostatic Bonding 523 Timothy Clark 18.1 Introduction 523 18.2 Anisotropic Molecular Electrostatic Potential Distribution Around Atoms 524 18.3 Electrostatic Anisotropy, Donor Acceptor Interactions and Polarization 528 18.4 Purely Electrostatic Models 530 18.5 Difference-Density Techniques 531 18.6 Directional Noncovalent Interactions 533 18.7 Conclusions 534 Acknowledgments 534 References 534 Index 537

Product Details

  • ISBN13: 9783527333158
  • Format: Hardback
  • Number Of Pages: 566
  • ID: 9783527333158
  • weight: 1216
  • ISBN10: 3527333150

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