sign in sign up
<<
Home , Carbometalation, Crystal Field Theory, Curie constant, Fluxional molecule, Ligand field theory, Metallic bonding

Encyclopedia of INORG ANIC Second Edition

Editor-in-Chief

R. Bruce King University of Georgia, Athens, GA, USA

Volume IX T-Z

WILEY Contents

VOLUME I Ammonolysis 236 Ammoxidation 236 Amphoterism 236 Ab Initio Calculations Analytical Chemistry of the Transition Elements 236 Acceptor Level Ancillary 248 Acetogen Anderson Localization 248 Catalyzed Reaction Angular Overlap Model 248 7r-Acid Ligand Anion 249 Acidity Constants Antiaromatic Compound 249 Acidity: Pauling's Rules 2 Antibonding 250 & Acidity 2 Antiferromagnetism 250 : Inorganic & Coordination Chemistry 2 Antigen 250 Actinides: 33 : 250 Activated Complex 59 Antimony: Organometallic Chemistry 258 Activation 59 Antioxidant 266 Activation Parameters 59 Antiport 266 Activation Volume 60 Antistructure 266 Active Site 60 Antitumor Activity 266 Adamson's Rules 60 Apoprotein 266 Addition Compound 60 Aqua 267 Agostic Bonding 60 Arachno Cluster 267 Alkali : Inorganic Chemistry 61 Arbuzov Rearrangement 267 Alkali Metals: Organometallic Chemistry 84 Archaea 267 Alkalides 94 Arene Complexes 267 Alkaline Earth Metals: Inorganic Chemistry 94 : Inorganic Chemistry 268 Alkaline Earth Metals: Organometallic Chemistry 116 Arsenic: Organoarsenic Chemistry 288 - Bond Activation 147 Arsine & As-donor 308 Complexes 153 Associative Substitution 309 Alkene Metathesis 154 Asymmetrie Synthesis 309 Alkene 154 Asymmetrie Synthesis by Homogeneous 309 Alkoxycarbonylation 154 Asymmetrie Unit 332 Complexes 154 Ate Complexes 332 Alkyl Migration 154 Transfer 332 Alkylidene 155 Atomic Mass 332 Alkylidyne 155 Atomic Number 332 Complexes 155 Atomization Enthalpy of Metals 332 Alkyne Metathesis 155 & 333 Allosterism 155 Aufbau Principle 333 Allotrope 156 Auger Spectroscopy 333 Alloys 156 Autoprotolysis 334 AUyl Complexes 169 Autoxidation 334 Alpha Helix 170 Alumina - 170 Back Bonding 335 Aluminum: Inorganic Chemistry 170 Bacteria 335 Aluminuni: Organometallic Chemistry 185 Bailar Twist 335 Ambidentate Ligand 210 Band Gap 336 Amide (Amido) Complexes 210 Band Theory 336 Ammonia & N-donor Ligands 210 :r- 336 XXII CONTENTS

BCS Theory 336 VOLUME II Becquerel 337 Bent 337 C-Terminus 603 Berry Pseudorotation 337 Cadmium: Inorganic & Coordination Chemistry 603 Beryllium: Inorganic Chemistry 337 Cadmium: Organometallic Chemistry 620 Beryllium & Magnesium: Organometallic Cage Effect 630 Chemistry 342 Calcium-binding Proteins 630 Beta Sheet 369 Calixarenes 666 Beta Turn 369 Carbanion 666 Bidentate Ligand 370 Carbene Complexes 666 Binary Compounds 370 Carbides: Transition -state Chemistry 674 Binding Energy of Nuclei 370 Carbocation 690 Bioavailability 370 690 Bioconjugate Chemistry 370 Carbon-Carbon & Carbon-Heteroatom Activation 690 Bioinformatics 370 Carbon: 696 370 Carbon: Inorganic Chemistry 718 Biomimesis 371 Carbon: Nanotubes 730 Biomimetic Synthesis of Nanoparticles 371 Carbonyl Complexes of the Transition Metals 764 Biomineralization 391 Carbonyl Compound 781 Biosynthesis 404 781 Biphasic Process 404 Carbonylation Processes by Homogeneous Catalysis 781 : Inorganic Chemistry 404 814 Carbyne Complexes 814 Bismuth: Organometallic Chemistry 425 Catalase 814 Bite Angle 440 Catalysis 815 Bleomycin 440 Catenation 815 5-Bond 440 Cation 815 7T-Bond 441 Cation-activated Enzymes 815 er-Bond 441 Ceramic 824 er-Bond Complexes 441 Ceramics 824 Bond Dissociation Energy 441 Chalcogenides: Solid-state Chemistry 825 Bond Energies 442 863 445 Chalcophiles 863 Bond Lengths in Inorganic & Liquids 446 Charge Carrier 864 a-Bond Metathesis 452 Charge Controlled Reactions 864 Bond Multiplicity 452 864 Bond Order 452 Charge Transfer 864 Bond Valence Method 453 Chauvin Mechanism 864 Bonding Energetics of Organometallic Compounds 453 Chelate Effect 865 Borates: Solid-state Chemistry 472 Chelating Ligands 865 Borazine 481 Chelation Therapy 865 Borides: Solid-state Chemistry 481 Chemical Bonding 865 Chemical Vapor Deposition 865 Born-Haber Cycle 494 Chevrel Phases 865 494 Chimie Douce 866 Boron: Inorganic Chemistry 499 Chiral 866 Boron: Metallacarbaboranes 524 Chiral Auxiliary 866 Boron: Metalloboranes 544 Chlorine, Bromine, Iodine, & Astatine: Inorganic Boron- Compounds 544 Chemistry 866 Boron: Organoboranes 560 Chlorophyll 887 Boron: Polyhedral 598 Chloroplast 887 Borosilicate Glass 601 : Biological Relevance 888 Bridging Ligand 601 Chromium: Inorganic & Coordination Chemistry 893 Brillouin Zone 602 Chromium: Organometallic Chemistry 907 Buckminsterfullerene 602 925 CONTENTS XXIII

Class A & Class B Behavior 925 Counter Ions 1226 Clathrate 925 Counting 1226 Clay Minerals 925 Coupling 1226 Close Packing 925 Covalent Bonds 1226 Closo Cluster 925 Covalent Radii 1227 Cluster 926 Crabtree's Catalyst 1227 Cluster Compounds: Inorganometallic Compounds Creutz-Taube Complex 1227 Containing. & Main Group Crossover Experiment 1227 Elements 926 Crown 1227 CNDO Calculations 947 Cryptands & Cryptates 1227 CO Insertion 947 Field Stabilization Energy 1228 Coalescence Temperature 947 1228 Cobaloxime 947 Crystal Orbital Overlap Population Curve 1229 Cobalt: B12 Enzymes & Coenzymes 947 Crystal Orbitals 1229 Cobalt: Inorganic & Coordination Chemistry 967 Crystal Structures 1230 Cobalt: Organometallic Chemistry 991 Crystallographic Radius 1230 1027 Crystallographic Shear 1230 Coenzyme 1027 Cupferron 1230 Collman's Reagent 1028 Cupredoxin 1230 Color 1028 Curie 1230 Common Anion Rule 1028 Curie Constant 1230 Competitive Inhibition 1028 1231 Compound 1028 Complexes of the Transition Metals 1231 Condensation 1029 1241 Conduction Band 1029 Cyclodextrins 1241 Conduction Band Edge 1029 Cyclodimerization & -trimerization Reactions 1241 Cone Angle 1029 Cyclometalation 1242 Configuration Interaction 1029 Cyclopentadienyl 1242 Cooper Pair 1029 Cymantrene 1242 Cooperativity 1030 Cytochrome Oxidase 1242 Coordination Chemistry: History 1030 Cytotoxicity 1254 Coordination Complexes 1053 Coordination Geometrie s 1053 Coordination Isomers 1053 VOLUME III Coordination Numbers & Geometries 1054 Coordination & Organometallic Chemistry: d" Configuration 1255 Principles 1065 d-d Transitions 1255 Coordination Theory 1081 d-Orbitals 1255 Coordinative Saturation & Unsaturation 1081 Dangling Bonds 1255 Coordinatively Inert & Labile Complexes 1081 Davies-Green-Mingos Rules 1256 Enzymes in Denitrification 1081 Deaminase 1256 Copper: Hemocyanin/Tyrosinase Models 1091 Decarbonylation Catalysis 1256 Copper: Inorganic & Coordination Chemistry 1100 Defects in Solids 1262 Copper: Organometallic Chemistry 1119 Degenerate Process 1281 Copper Proteins: Oxidases 1134 Dehydratase 1281 Copper Proteins with Dinuclear Active Sites 1159 Dehydrogenase 1281 Copper Proteins with Type 1 Sites 1173 Delocalized Bonding 1281 Copper Proteins with Type 2 Sites 1201 Deltahedron 1281 Corands 1225 Density Functional Theory 1281 Core Orbitals 1225 Density of States 1282 Correlation Diagram 1225 Derivative Structure 1282 Cossee-Arlman Mechanism 1225 Descent in Symmetry 1282 Cotton Effect 1226 Deuterium 1282 Cotton-Kraihanzel Force Field 1226 Deuteron 1282 Coulombic Interaction 1226 Dewar-Chatt-Duncanson Bonding Model 1282 XXIV CONTENTS

Diamagnetism 1283 Transfer in Coordination Compounds 1388 Diastereotopy 1283 Electron Transfer Reactions: Theory 1410 Dielectric Polarizabilities of Oxides & 1284 Electron Transport Chains 1425 Diene Complexes 1291 1426 Differential Scanning Calorimetry 1291 Electroneutrality 1427 Diffraction Methods in Inorganic Chemistry 1292 Electronic Spectroscopy 1427 Dihydrogen Complexes & Related Sigma Electronic Structure of Main-group Compounds 1427 Complexes 1327 Electronic Structure of Organometallic Diketones 1332 Compounds 1455 Dinitrogen & Dinitrogen Complexes 1332 Electronic Structure of Solids 1480 Dinuclear 1332 Electronic Structure of Clusters 1506 Dinuclear Organometallic Cluster Complexes 1333 Electronic Transition 1525 Dinucleating Ligand 1359 1525 Dioxygen & Related Ligands 1359 Electrophilic Reaction 1525 Dioxygenase 1367 Electrostatic Bond Strength 1525 Diphenolase 1367 a -Elimination 1526 Dipole Moment 1367 ß-Elimination 1526 Dipoles & Dipolar Effects 1367 Ellingham Diagram 1526 Direct Band Gap 1368 Enantioselectivity 1526 Disproportionation 1368 End-On Coordination 1527 Dissociation 1368 Endothermic Reaction 1527 Distortion Isomerism 1368 Energy Bands 1527 Bridge 1368 Energy Factored Force Field 1528 Dithiocarbamate 1368 Entatic State 1528 Dithiolenes 1368 Enthalpy 1528 DNA Polymerase 1369 Entropy 1528 Dodecahedral 1369 Enzyme 1528 a -Donor 1369 Enzyme Commission 1528 Donor Atom 1369 Equilibrium Constant 1528 Donor Level 1369 Eubacteria 1529 Double Insertion 1369 Eukaryote 1529 Double Salt 1369 Evans Method 1529 Drago Parameters 1370 Excited State 1529 Drago-Wayland Scheme 1370 EXELFS 1529 Exo & Endo 1529 (E) & (Z) Isomers 1373 Exothermic Reaction 1530 Effective Atomic Number Rule 1373 Expanded Octet 1530 Eighteen Electron Compounds 1373 Extended Hückel 1530 Electrides 1374 Extended Structures 1530 Electrochemical Series 1374 Extended X-ray Absorption Fine Structure 1530 : Applications in Inorganic Extraction of the Elements 1530 Chemistry 1374 Electrode Potentials 1379 f-Block Metals 1531 Electron Affinity 1384 F-center 1531 Electron Configuration 1385 f-Orbitals 1531 1387 Fajans' Rules 1531 Electron Deficient Compound 1387 Fan Angle 1532 Electron Deformation Density 1387 Faujasite 1532 Electron Microscopy 1387 Fenske-Hall Method 1532 Electron Nuclear Double Resonance Spectroscopy 1387 Fenton Chemistry 1532 Electron Paramagnetic Resonance 1387 Fermi Level 1532 Electron Precise Compound 1388 Fermi Surface 1532 Electron Rieh Compound 1388 Ferrimagnetism 1532 Electron Spectroscopy for Chemical Analysis 1388 Ferrite 1532 Electron Spin Echo Envelope Modulation 1533 Spectroscopy 1388 Ferroelectricity 1533 CONTENTS XXV

Ferromagnetic Insulator 1533 Haptomers 1762 Ferromagnetism 1533 Hard & Soft Acids and Bases 1762 Ferroxidase 1533 Hartree-Fock Theory 1766 Field Microscopy 1534 Heck Arylation 1767 Fischer-Hafner Synthesis 1534 1767 Fischer-Tropsch Process 1534 Heitier-London Wavefunction 1767 Fischer-type Carbene Complexes 1534 Herne Proteins 1767 Fischer-type Carbyne Complexes 1535 Heptadentate 1767 Fissile Isotope 1535 Heterogeneous Catalysis by Metals 1768 Fission Product 1535 Heterogenized Catalyst 1784 Flash Photolysis 1535 Heteroleptic Compound 1784 Fluorescence 1535 Heterolytic Cleavage 1784 Fluorides: Solid-state Chemistry 1535 Hexadentate 1784 Fluorine: Inorganic Chemistry 1561 High Performance Liquid Chromatography 1784 Fluorocarbons: Organometallic Derivatives 1585 High Pressure Synthesis of Solids 1785 Fluxional 1585 High Resolution Electron Energy Loss Force Constant 1585 Spectroscopy 1800 Formal Charge 1586 High-spin & Low-spin Compounds 1800 Formal 1586 High-temperature Limit 1801 Fourier Transform 1586 High-temperature 1801 Fragment Orbitals 1586 Holes 1801 Free Electron Theory 1586 Holoprotein 1802 Frenkel Defects 1587 Homeostasis 1802 Frequency Factored Force Field 1587 HOMO 1802 Frontier Orbitals 1587 HOMO-LUMO Gap 1802 Fuoss-Eigen Equation 1587 Homoleptic Compound 1802 Homologation Reactions 1802 g-Factor 1589 Homolytic Cleavage 1802 : Inorganic Chemistry 1589 Hot-atom Chemistry 1802 Gallium: Organometallic Chemistry 1621 Hückel Theory 1803 Gene 1629 Hund's Rules 1804 Gene Expression 1629 Hybridization 1804 Genetic Engineering 1629 Hydrated Electron 1804 Genetic Regulation 1629 Hydrated Ions 1804 : Inorganic Chemistry 1630 Hydrates 1805 Germanium: Organometallic Chemistry 1650 Hydrazides 1805 Gibbs Energy 1673 Complexes of the Transition Metals 1805 Glycoprotein 1673 0-Hydride Elimination 1813 Gold: Inorganic & Coordination Chemistry 1673 Hydrides 1813 Gold: Organometallic Chemistry 1688 Grain Boundary 1698 Hydrides: Solid State Transition Metal Complexes 1814 Greenhouse Effect 1698 Hydroboration 1846 Green-Rooney Mechanism 1698 Hydroboration Catalysis 1847 Grignard Reagents 1698 Hydrocarbyl 1855 Ground State 1698 Hydrocyanation 1855 Group 14 Multiple Bonding 1698 Hydrocyanation by Homogeneous Catalysis 1855 Group Numbering System 1739 Hydrodesulfurization & Hydrodenitrogenation 1860 Group Theory 1739 Hydroformylation 1877 Hydrogen Bonding 1877 Haber Process 1741 Hydrogen Bonding & Dihydrogen Bonding 1878 Half-sandwich Complexes 1741 Hydrogen: Inorganic Chemistry 1882 Halides: Solid-state Chemistry 1741 Hydrogenase 1906 Hall-Herault Process 1761 Hydrogenation 1906 & Complexes 1761 Hydrogenation & Isomerization of 1907 Haloperoxidases 1761 Hydrometalation 1925 1761 Hydron 1926 XXVI CONTENTS

Hydronium Ion 1926 : Models of Proteins with Dinuclear Active Hydrophilicity 1926 Sites 2295 Hydrophobicity 1926 Iron: Organometallic Chemistry 2307 Hydrosilation 1926 Iron Porphyrin Chemistry 2390 Hydrosilation Catalysis 1926 Iron Proteins for Storage & Transport & their Hydrozirconation 1938 Synthetic Analogs 2521 1938 Iron Proteins with Dinuclear Active Sites 2542 Hypercoordination 1938 Iron Proteins with Mononuclear Active Sites 2557 Hypervalent Compounds 1938 Iron-Sulfur Models of Protein Active Sites 2578 Iron-Sulfur Proteins 2589 Iron Transport: Siderophores 2619 VOLUME IV Irving-Williams Series 2646 Isocarbonyl Complexes 2646 Isocyanide Ligands 2646 Icosahedron 1961 Isoelectronic 2647 Imide Complexes 1961 Isolobal Analogy 2647 Immunochemistry 1961 Isomer Shift 2647 In Situ Reaction 1961 Isomer, Types of 2647 Incommensurate Structure 1961 Isomorphous 2647 Indirect Band Gap 1961 Isosbestic Point 2648 Indium: Inorganic Chemistry 1962 Isosteric Groups 2648 Indium: Organometallic Chemistry 1979 Isotope Effect 2648 Inert Pair Effect 2027 Isotopes & Isotope Labeling 2648 Infrared Reflection Spectroscopy 2027 Isotopic Perturbation of Resonance 2649 Infrared Spectroscopy 2027 Isotopomer 2649 Inhibition Constant 2027 Inhibitor 2027 Inner-sphere Reaction 2028 VOLUME V Inorganic Heterocycle 2028 Inorganic Ring Systems 2028 Jahn-Teller Effect 2651 Insertion 2055 Insulator 2056 Kaminsky Catalysts 2655 Intercalation Chemistry 2056 Kapustinskii Equation 2655 Interchange Mechanism of Substitution 2092 Kinetic Lability 2655 Intergrowth Structures 2092 Kinetic Methods 2655 2092 Kinetic Stability 2655 2656 Intermolecular 2092 Klechkowsky's Rule Koopman's Theorem 2656 Intersystem Crossing 2093 Intervalence Transfer Transition 2093 Labile 2657 Intramolecular 2093 Contraction 2657 Ion Exchange 2093 Laporte Rule 2657 Ion Pairing 2093 Latimer Diagrams 2657 Ionic Bonds 2093 Lattice Energy 2657 Ionic Character 2093 LCAO Approximation 2658 Ionic Conductors 2094 : Inorganic Chemistry 2658 Ionization Potential 2127 Lead: Organometallic Chemistry 2671 Iridium: Inorganic & Coordination Chemistry 2130 Leaving Group 2680 Iridium: Organometallic Chemistry 2148 Leveling Effect 2680 Iron: Herne Proteins & Dioxygen Transport & Lewis Acids & Bases 2680 Storage 2167 Lifetime Broadening 2680 Iron: Herne Proteins & Electron Transport 2180 Ligand 2681 Iron: Herne Proteins, Mono- & Dioxygenases 2200 2681 Iron: Herne Proteins, Peroxidases, Catalases & Ligand Field Theory & Spectra 2681 Catalase-peroxidases 2229 Ligand Substitution 2700 Iron: Inorganic & Coordination Chemistry 2250 Ligand-to-Metal Charge Transfer 2700 CONTENTS XXVII

Lime 2700 Metal-mediated Protein Modification 3052 Linkage Isomerism 2700 Metal Nanoparticles, Organization & Applications Liquid Crystal 2701 of 3065 Lithophiles 2701 Metal Nanoparticles, Synthesis of 3083 Localized Bonding 2701 Metal-Organic Chemical Vapor Deposition 3096 Localized & Delocalized Orbital Descriptions 2701 Metal-related Diseases of Genetic Origin 3096 Lone Pair 2702 Metal Storage 3109 Long-range Electron Transfer in Biology 2702 Metal Vapor Synthesis of Transition Metal Low Coordinated Group 13 Chelates 2714 Compounds 3110 Low-energy Electron Diffraction 2718 3121 Low Oxidation State Main Group 2718 3121 Low Temperature Limit 2730 Metallic Deposition: Metal-organic Luminescence 2730 Precursors 3121 Luminescence Behavior & Photochemistry of Complexes 3144 Organotransition Metal Compounds 2748 Metallocenter Biosynthesis & Assembly 3144 LUMO 2779 Metallochaperones & Metal Ion Homeostasis 3152 3158 Metallole 3158 Macrocycle 2781 Metalloporphyrin 3159 Macrocyclic Ligands 2781 Metalloprotein 3159 Madelung Constant 2800 Metalloprotein Design & Engineering 3159 Magnetic Circular Dichroism 2801 Magnetic Oxides 2801 Metalloregulation 3193 Magnetic Susceptibility 2836 Metallothioneins 3208 3221 of Extended Arrays in Inorganic Solids 2836 Metals Magnetism of Transition Metal Ions 2859 Metathesis 3221 2869 Metathesis Polymerization Processes by Main Group Carbenes 2870 Homogeneous Catalysis 3222 Main Group Elements 2888 Methanogen 3233 Main Group: Multiple Bonding 2888 Michaelis Constant 3233 Manganese: Inorganic & Coordination Chemistry 2894 Michaelis-Menten Kinetics 3233 Manganese: Organometallic Chemistry 2907 Microstates 3233 Manganese Proteins with Mono- & Dinuclear Sites 2922 Microwave Spectroscopy 3233 Manganese: The -evolving Complex & 3233 Models 2932 3234 Marcus Equation 2947 Mineralomimetic 3234 Marcus Treatment 2947 Mixed Donor Ligands 3234 Mass Defect 2947 Mixed Oxidation States 3255 Mass Spectrometry 2948 Mixed Valence Compounds 3255 Matrix Isolation 2948 Mixed Valence Compounds, Classification 3267 Mechanisms of Reaction of Organometallic Moh's Hardness 3268 Complexes 2948 Molecular Beam Epitaxy 3268 Melanins 2968 Molecular Biology 3268 Membrane 2968 Molecular Mechanics 3268 : Inorganic & Coordination Chemistry 2968 Molecular Orbital Stabilization Energy 3268 Mercury: Organometallic Chemistry 2983 Molecular Orbital Theory 3269 Mercury Photosensitization 2992 Molecular Orbitals 3292 Metabolism 2992 Molybdenum: Inorganic & Coordination Chemistry 3293 Metal Analysis 2992 Molybdenum: MPT-containing Enzymes 3321 Metal-based Drugs 2992 Molybdenum: Organometallic Chemistry 3340 Metal-based Imaging Agents 3020 Mond Process 3358 Clusters 3040 Monodentate Ligand 3358 Metal Carbonyls - 3040 Monooxygenase 3358 Metal Clusters 3040 Monophenolase 3358 Metal-Insulator Transitions 3040 Monsanto Acetic Acid Process 3359 Metal Ion Toxicity 3041 Mössbauer Spectroscopy 3359 I

XXVIII CONTENTS

Mott-Hubbard Transition 3359 Nucleus 3725 Mulliken-Hund Wavefunction 3359 Nutritional Aspects of Metals & Trace Elements 3725 Multicenter Two-electron Bonding 3359 Nyholm-Gillespie Model 3732 Multi-Heme Cytochromes & Enzymes 3360 Mutation 3376 Octahedral 3733 Octet Rule 3733 VOLUME VI Oligomer 3733 Oligomerization & Polymerization by Homogeneous Catalysis 3733 N-Heterocyclic Carbene 3377 One-dimensional Metal 3749 N-Terminus 3377 Orbitally Controlled Reactions 3750 Nanocrystals 3377 Order-Disorder Transition 3750 Nanoparticle 3377 3377 Organic Light-emitting Diode 3750 Nernst Equation 3378 Using Metal-mediated Coupling Enzymes & Cofactors 3378 Reactions 3750 Nickel: Inorganic & Coordination Chemistry 3393 Organic Synthesis Using Metal-mediated Nickel: Models of Protein Active Sites 3425 Metathesis Reactions 3770 Nickel: Organometallic Chemistry 3442 Organic Synthesis using Organometallic 3462 Reagents of Group 1, 2, 11, & 12 Metals 3815 Nido Cluster 3462 Organic Synthesis using Transition Metal Carbonyl Nineteen Electron Configuration 3462 Complexes 3815 Niobium & Tantalum: Inorganic & Coordination Organic Synthesis using Transition Metal Chemistry 3462 Complexes Containing jr-Bonded Ligands 3880 Niobium & Tantalum: Organometallic Chemistry 3487 Organoelement Chemistry 3935 Nitride Complexes 3515 Organometallic Chemical Vapor Deposition 3935 Nitrides: Transition Metal Solid-state Chemistry 3515 Organometallic Complexes 3935 Nitrogen Fixation 3531 Origin of the Elements 3936 Nitrogen: Inorganic Chemistry 3531 ORTEP Diagram 3936 Nitrogen Monoxide (Nitric Oxide): Bioinorganic Orthometalation 3936 Chemistry 3601 Osmium: Inorganic & Coordination Chemistry 3936 Nitrogenase Catalysis & Assembly 3621 Osmium: Organometallic Chemistry 3960 Nitrogenase: Metal Cluster Models 3637 3977 Nitrosyl Complexes 3650 Outer-sphere Reaction 3977 Noble Gases: Inorganic Chemistry 3651 Overlap Integral 3977 Node 3670 Overpotential 3978 Nomenclature 3670 Oxidation Catalysis by Transition Metal Complexes 3978 Nonclassical Hydrides 3670 Oxidation Number 3984 Noncoordinating Anion or Cation 3670 3984 Noncrossing Rule 3670 Oxidative Coupling 3985 Noncrystalline Solids 3670 Oxidative Phosphorylation 3985 Nonlinear Optical Materials 3688 Oxide Catalysts in Solid-state Chemistry 3985 Nonstoichiometric Compounds 3688 Normant Complexes 3689 Oxides: Solid-state Chemistry 4006 Nuclear Chain Reactions 3689 Oxidoreductase 4053 Nuclear Explosives 3689 /i-Oxo Bridge 4053 Nuclear Fuels 3689 Oxo Complex 4053 Nuclear Magnetic Resonance 3690 Oxo Process 4053 Nuclear Quadrupole Coupling Constant 3690 Oxo Transfer 4054 Nuclear Quadrupole Resonance Spectroscopy 3690 Oxoanion 4054 Nucleic Acid-Metal Ion Interactions 3690 Oxophilic Character 4054 Nucleic Acids 3724 Oxygen Activation 4054 Nucleon 3724 Oxygen: Inorganic Chemistry 4054 3724 Oxygenase 4100 : Rules for Predicting Direction 3724 & Ozone Layer 4100 CONTENTS XXIX

VOLUME VII Podandocoronands 4543 Podands 4543 Polar Bonds 4543 pjr-d* Bonding 4101 Polar Compounds 4543 P-donor Ligands 4101 Polarizability 4544 p-Orbitals 4128 Polaron 4544 : Inorganic & Coordination Chemistry 4128 : Inorganic Chemistry 4544 Palladium: Organometallic Chemistry 4147 Polonium: Organometallic Chemistry 4551 Paramagnetic Organometallic Complexes 4188 Polyacrylamide Gel Electrophoresis 4554 4200 Polyhedra 4554 Pauli Principle 4200 Polyhydride 4557 Pauling's Rules 4201 Polymer 4558 Pauson-Khand Reaction 4201 Polymerase Chain Reaction 4558 Pearson Symbols 4201 Polymerization 4558 Peierls Distortion 4201 Polymorph 4558 Pendant Groups 4202 Polynuclear Complexes 4558 Pentadentate Ligand 4202 Polynuclear Organometallic Cluster Complexes 4558 Pentadienyl Ligand 4202 Polyoxometalates 4575 Pentagonal Bipyramid 4202 Polypeptide 4586 4202 Polyphosphazenes 4586 Peptide-Metal Interactions 4202 Polyprotic Acid 4593 4216 Polysiloxanes & Polysilanes 4593 Periodic Table: Historical Aspects 4216 Porous Inorganic Materials 4611 Periodic Table: Trends in the Properties of the Porphyrin 4631 Elements 4226 Post-Translational Modification 4631 Peroxidases 4239 Pourbaix Diagram 4632 Peroxide 4239 Primary Structure 4632 Peroxo Complexes 4239 Prokaryote 4632 Perturbation Theory 4239 Prosthetic Group 4632 Diagram 4240 Protein Determination 4633 Phase Rule 4240 Protein Structure by NMR 4633 Phase Transfer Catalyst 4240 Proton 4633 Phosphates: Solid-state Chemistry 4240 Proton Coupled Electron Transfer 4633 Phosphazenes 4255 Protonation 4634 Phosphides: Solid-state Chemistry 4255 Protoporphyrin 4634 Phosphorescence 4308 Prassian Blue 4634 : Inorganic Chemistry 4308 Pseudohalide 4634 Phosphorus-Nitrogen Compounds 4329 Pseudorotation 4634 Phosphorus: Organophosphorus Chemistry 4355 Pulse Radiolysis 4634 Photochemistry 4373 Purex Separation Scheme 4635 Photochemistry of Transition Metal Complexes 4373 Photochemistry of Transition Metal Complexes: Quadridentate Ligand 4637 Theory 4418 Quadrupolar 4637 Photochromism 4432 Quantum Dots 4637 Photoconductivity 4432 Quantum Mechanical Tunneling 4637 Photoelectron Spectroscopy of Transition Metal Quantum-size Effect 4637 Systems 4432 Quantum Yield 4637 Photosensitization 4459 Quasicrystals 4638 Photosynthesis 4459 Photosystem I 4487 Racah Parameter 4641 Piano Stool Structure 4487 Radiation Chemistry 4641 Picolinic Acid 4487 Radicals 4641 Platinum-based Anticancer Drugs 4488 Radioactive Decay 4641 Platinum: Inorganic & Coordination Chemistry 4499 Radioisotope Generators 4641 Platinum: Organometallic Chemistry 4507 Raft Clusters 4642 Pnictide 4543 Raman Spectroscopy 4642 XXX CONTENTS

Rare Earth Elements 4642 : Inorganic Chemistry 4931 Ray-Dutt Twist 4642 Selenium: Organoselenium Chemistry 4956 Reaction Center 4642 Selenium Proteins Containing 4970 Recoil Chemistry 4643 Self-assembled Inorganic Architectures 4980 Recombinant DNA 4643 Self-assembly 5025 Red Lead 4643 Self-assembly: Bioinorganic 5025 Redistribution Reaction 4643 Self-exchange Reaction 5025 Potential 4643 Semi Empirical Theoretical Methods 5025 Redox Properties & Processes 4643 Semibridging Carbonyl Ligand 5025 Reductase 4644 Semicarbazide 5025 Reduction 4644 Semiconductor Interfaces 5026 Reductive C-C Coupling 4644 Semiconductor Nanocrystal Quantum Dots 5042 Reductive Carbonylation 4644 5063 Reductive Coupling 4644 Semimetal 5079 Reductive Elimination 4645 Sequencing 5079 Reductive Ligation 4645 Seventeen Electron Configuration 5079 Regiochemistry 4645 Shift Reaction 5079 Regioselectivity 4646 Short-lived Intermediates 5080 Relativistic Effects 4646 Side-on Coordination 5109 Reorganizational Energy 4646 Siderophiles 5109 Replication 4646 Silica 5109 Reppe Reaction 4646 : Inorganic Chemistry 5109 Resonance Raman Spectroscopy 4646 Silicon: Chemistry 5158 Rhenium: Organometallic Chemistry 4647 : Inorganic & Coordination Chemistry 5187 Rhodium: Inorganic & Coordination Chemistry 4693 Silver: Organometallic Chemistry 5197 Rhodium: Organometallic Chemistry 4722 Simmons-Smith Reaction 5203 Ring Opening Metathesis Polymerization Singlet State 5204 Reactions 4756 Siroheme 5204 Ring Whizzers 4756 Skeletal Bonding Electrons 5204 RNA Polymerase 4756 Slip Processes in Ligands 5204 Robin & Day Scheme 4756 Small-angle X-ray Scattering 5204 Ruthenium: Inorganic & Coordination Chemistry 4757 Smelting 5205 Ruthenium: Organometallic Chemistry 4778 Sol-Gel Encapsulation of Metal and Semiconductor Nanocrystals 5205 Sol-Gel Synthesis of Solids 5213 VOLUME VIII Solid Solution 5224 Solids: Characterization by Powder Diffraction 5224 S-donor Ligands 4811 Solids: Computer Modeling 5242 s-Orbitals 4837 Solids: Defects 5258 Sacrificial Anode 4837 Solvolysis 5258 4837 Sonication 5258 Saturation, Coordinative 4837 5258 Scandium, Yttrium & the : Inorganic & Soret Band 5259 Coordination Chemistry 4838 Specific Activity 5259 Scandium, Yttrium & the Lanthanides: Specific Radioactivity 5259 Organometallic Chemistry 4878 Spectator Ligand (Ion) 5259 Scanning Tunneling Microscope 4930 Spectrochemical Series 5259 Schiff Base 4930 Spherands 5259 Schlenk Tube 4930 Spin Saturation Transfer 5260 Schottky Defects 4930 Spineis 5260 Schrock-Osborn Catalyst 4930 Spirocyclic Compound 5260 Schrock-type Carbene Complexes 4930 Splitting, Crystal Field & Molecular Orbital 5260 Schrock-type Carbyne Complexes 4931 Square Antiprism 5260 Schwartz's Reagent 4931 Square Planar 5260 Secondary Ion Mass Spectrometry 4931 Square Pyramidal 5261 CONTENTS XXXI

Stability Constants & their Determination 5261 Thallium: Organometallic Chemistry 5569 Staudinger Reaction 5269 Thermite Reaction 5581 Steady-state Kinetics 5269 Thermochromism 5581 Steam-reforming Process 5269 Thermodynamics: Laws 5581 Stereochemical Nonrigidity of Organometallic Thermogravimetric Analysis 5581 Complexes 5270 Thin Film Synthesis of Solids 5582 Stereochemistry 5303 Thiocarbonyl 5589 Stereolability 5303 Thiometalates 5589 5303 Thionitrosyl 5590 Steric Effect 5303 Thiourea 5590 Steric Requirement 5304 Three-center Bond 5590 Steric Saturation or Unsaturation 5304 Tight-binding Approximation 5590 Stille Coupling 5304 Timescale 5590 Stoner Criterion 5304 : Inorganic Chemistry 5590 Structure & Property Maps for Inorganic Solids 5305 Tin: Organometallic Chemistry 5605 Strukturbericht Symbols 5323 Titanium: Inorganic & Coordination Chemistry 5634 Substrate 5324 Titanium: Organometallic Chemistry 5644 Subunit 5324 Titanocene 5674 Subvalent Compounds 5325 Tolman's Cone Angle 5674 Sulfur: Inorganic Chemistry 5342 Topotactic 5674 Sulfur-Nitrogen Compounds 5378 Trace Element 5674 Sulfur: Organic Polysulfanes 5403 Trans Effect 5674 Sum Frequency Generation 5435 Trans Influence 5674 Superacid 5435 Transannular Bonding 5675 Superconductivity 5435 Transcription Factor 5675 Superconductivity in Solids 5448 Transition Metal Carbonyls: Infrared Spectra 5675 Superexchange 5448 Transition Metal Complexes with Bulky AUyl Superoxide 5448 Ligands 5690 Superoxide Dismutase 5449 Transition Metals 5695 Supported Organotransition Metal Compounds 5449 5695 Surface Enhanced Raman Scattering 5458 Transmission Electron Microscopy 5696 Surface States 5458 Tribology 5696 Surfaces 5458 Tridentate Ligand 5696 Suzuki Coupling 5483 Trigonal Bipyramidal 5696 Symmetry Adapted Linear Combinations 5483 Trigonal Prism 5696 Triple-decker Sandwich 5696 Symmetry Point Groups 5485 Triplet State 5697 Symport 5488 Tripodal Ligand 5697 Synergie Bonding 5488 Tris(pyrazolyl)borates 5697 Synthesis Gas 5488 Tritium 5697 : Inorganic & Coordination Chemistry 5697 VOLUME IX Tungsten: Organometallic Chemistry 5722 Tungsten Proteins 5743 Turnover 5751 Ti Method 5489 Turnstile Mechanism 5751 Tanabe-Sugano Diagram 5489 Tebbe's Reagent 5490 Uniport 5753 Technetium: Organometallic Chemistry 5490 Uranocene 5753 Technetium & Rhenium: Inorganic & UV-Visible Spectroscopy 5753 Coordination Chemistry 5499 : Inorganic Chemistry 5516 Vacant Site 5755 Tellurium: Organotellurium Chemistry 5539 Valence Band 5755 Templating ' 5557 Valence Band Edge 5755 Tetradentate Ligand 5557 Valence Bond Theory 5755 Tetrahedral 5557 Valence Orbitals 5755 Thallium: Inorganic Chemistry 5557 Valence Shell Repulsion Model 5755 XXXII CONTENTS van der Waals Forces 5756 Ylide 5829 Vanadium in Biology 5756 Vanadium: Inorganic & Coordination Chemistry 5767 Zeise's Salt - 5831 Vanadium: Organometallic Chemistry 5784 Zeolites 5831 Vanadocene 5803 Zero Point Energy 5867 Vaska's Complex 5804 Ziegler-Natta Catalysts 5867 Vibronic Coupling 5804 Zinc: DNA-binding Proteins 5867 Vicinal 5804 Zinc Enzymes 5885 Vitamin 5804 Zinc Finger 5927 Zinc: Inorganic & Coordination Chemistry 5928 Wacker Process 5805 Zinc: Organometallic Chemistry 5953 Wade's Rules 5805 Zintl Border 6006 Walsh Diagram 5806 Zintl Compounds 6006 Wannier Functions 5806 & Hafnium: Inorganic & Coordination Water Exchange 5806 Chemistry 6014 Water Gas Reaction 5807 Zirconium & Hafnium: Organometallic Chemistry 6038 Water & O-donor Ligands 5807 ZSM 6076 Wavefunction 5825 Zwitterion 6076 Werner Complexes 5825 Wilkinson's Catalyst 5825 Wittig Reagent 5825 VOLUME X Wolfsberg-Helmholz Relationship 5825 Woodward-Hoffmann Rules 5825 Abbreviations and Acronyms 6077

X-ray Absorption Spectroscopy 5827 6089 X-ray Crystallography 5827 List of Contributors X-ray Diffraction 5827 XANES 5827 Index 6111