Comprehensive Coordination Chemistry II - From Biology to Nanotechnology 2 ed. in 10 Vol.Set Volume 01 - Fundamentals - Ligands, Complexes, Synthesis, Purification, and Structure

McCleverty J.A. (ed.) Comprehensive Coordination Chemistry II - From Biology to Nanotechnology 2 ed. in 10 Vol.Set Volume 01 - Fundamentals - Ligands, Complexes, Synthesis, Purification, and Structure 2003 [pdf 819sc 806+1c. 11.35mb]Comprehensive Coordination Chemistry II (CCC II) is the sequel to what has become a classic in the field, Comprehensive Coordination Chemistry, published in 1987. CCC II builds on the first and surveys new developments authoritatively in over 200 newly comissioned chapters, with an emphasis on current trends in biology, materials science and other areas of contemporary scientific interest.Table of Contents:Volume 1: Fundamentals: Ligands, Complexes, Synthesis, Purification, and StructureSection I: LigandsSection II: Synthesis, Purification, and Characterization of Coordination CompoundsSection III: Reactions of Coordinated LigandsSection IV: Stereochemistry, Structure, and Crystal EngineeringSection V: New Synthetic MethodsVolume 2: Fundamentals: Physical Methods, Theoretical Analysis, and Case StudiesSection I: Physical MethodsSection II: Theoretical Models, Computational Methods, and SimulationSection III: SoftwareSection IV: Case StudiesVolume 3: Coordination Chemistry of the s, p, and f MetalsVolume 4: Transition Metal Groups 3–6Volume 5: Transition Metal Groups 7 and 8Volume 6: Transition Metal Groups 9–12Volume 7: From the Molecular to the Nanoscale: Synthesis, Structure, and PropertiesVolume 8: Bio-coordination ChemistryVolume 9: Applications of Coordination ChemistryVolume 10: Indexes Cover Page 1 Editors-in-Chief 2 Volume Editors 3 International Advisory Board 4 Preface 5 Comprehensive Coordination Chemistry Mapping Tables 6 Coordination Chemistry: The Past, Present, and Possible Future 15 Introduction to Volumes 1 and 2 17 Introduction to Volume 3 18 Introduction to Volume 4 19 Introduction to Volume 5 20 Introduction to Volume 6 21 Introduction to Volume 7 22 Introduction to Volume 8 30 Introduction to Volume 9 31 Permission Acknowledgments 33 COMPREHENSIVE COORDINATION CHEMISTRY II 34 Volumes 35 Info on Volume 1 36 Volume 1 38 Secton I - Ligands 38 1.1 Bipyridine Ligands 38 Introduction 38 Synthesis of the Bipyridine Ring System 39 Traditional Methods 39 Metal-catalyzed Coupling Reactions 39 Homocoupling of halopyridines 39 Cross-coupling of halopyridines with pyridyl organometallics 40 Preparation from Acyclic Precursors 41 Krohnke method 41 Cycloaddition methods 41 Other Synthetic Methods 42 Reactions of the Basic Bipyridine Ring System 43 Oxidation and Reduction 43 Substitution 43 Functionalized Bipyridines: Synthesis and Uses of Common Building Blocks 43 Hydrocarbons 45 Halomethyl Derivatives 47 Acid Derivatives 47 Unsymmetrical Derivatives 48 Chiral Bipyridines 49 Synthesis 49 Asymmetric Catalysis 50 Macrocycles 50 Bipyridines with Pendant Macrocycles 50 Bipyridines in the Macrocycle 51 Multidentate Chelates 51 Polymers 52 Macroligands 52 Bipyridines in the Main Chain 52 Polymers with Bipyridine Side Chains 53 Bipyridines and Biological Molecules 53 Peptides 53 Carbohydrates 53 Nucleic Acids 54 Bipyridine Analogues 54 Biquinolines 54 Biisoquinolines 54 Other Analogues 55 References 55 1.2 Phenanthroline Ligands 61 Introduction 61 Introduction and Basic Transformations 61 Halogenation 62 Oxidative Substitutions 63 Alkylation and Catalyzed Cross-coupling 63 Research Trends Among Phenanthroline Complexes 64 Bioconjugates 64 Chiral Phenanthrolines 64 Molecular Recognition and Phenanthroline-based Ionophores 64 Chromophore-containing Phenanthrolines 65 Electroactive Ligands 67 Oligophenanthrolines 67 Polymer Supports for Phenanthrolines 70 Phenanthroline-based Dendrimers 71 References 72 1.3 Terpyridine, Oligopyridine, and Polypyridine Ligands 76 Introduction and Scope 76 Parent System And N-Oxides 77 Monosubstituted Terpyridines 77 4 ́-Substituted 77 4-Substituted 79 6-Substituted 79 Disubstituted Terpyridines 81 3, ́ ́-Disubstituted 81 4,4 ́-Disubstituted 81 5,5 ́-Disubstituted 82 6,6 ́-Disubstituted 82 3 ́,4 ́-Disubstituted 83 Trisubstituted Terpyridines 83 Tetrasubstituted Terpyridines 84 Fused (Annelated) Terpyridines 84 Benzo-fused 84 Other Fused 84 Oligopyridines 86 References 87 1.4 Pyridopyridine Ligands 89 Introduction 89 Complexes with the 1,8-Naphthyridine Ligand 89 Complexes with Functionalized Derivatives of the 1,8-Naphthyridine Ring 90 Other Multidentate Ligands Derived from the 1,8-Naphthyridine Ring 93 References 94 1.5 Heterocyclic and Open-chain 1,2-Diazine Ligands 96 Introduction and Scope 96 Pyridazine- and Phthalazine-Derived Ligands 97 Overview 97 Ligand Preparations 98 Pyridazine-derived ligands 98 From halopyridazines 98 From pyridazine-carbaldehydes and pyridazine-ketones 99 From 1,2,4,5-tetrazines 101 Phthalazine-derived ligands 103 Preparation of precursors: 1,4-dihalophthalazines, 1,4-dicyanophthalazine, and 1,4-dihydrazinophthalazine 103 From 1,4-dihalophthalazines 105 From 1,3-(substituted-pyridylimino)isoindolines 105 From 1,4-dihydrazinophthalazine 105 Condensed phthalazine-derived ligands 106 Coordination Chemistry 107 Open-Chain Diazine Ligands 109 Overview 109 Preparation 111 Preparation of precursors: imidates, amide hydrazones, and hydrazides 111 Amide hydrazones (amidrazones) and hydrazides 112 Ligand Preparations 112 Type 8; mixed diazine (N-N) ligands 121 Coordination Chemistry 121 Concluding Remarks 123 References 126 1.6 Beta-Diketones and Related Ligands 129 Introduction 129 Main Fields of Research on Technological Applications of Metal beta-Diketonates 130 Structure and Tautomerism of beta-Diketones 130 Synthesis of beta-Diketones 131 Coordination Modes of beta-Diketones 133 Neutral beta-diketones 134 Monoanionic beta-diketonates 134 Dianionic beta-diketonates 135 Syntheses of Metal Diketonates 135 Synthesis from Metals 135 Synthesis from Metal Halides 136 Synthesis from Organometallic Halides 136 Synthesis from Metal Acetates, Nitrates, Sulfates, or Carbonates 136 Synthesis from Metal or Organometallic Oxides 137 Synthesis from Metal or Organometallic Alkoxides 137 Synthesis from Metal Carbonyl 137 Synthesis from Metal Alkyls or Aryls 137 Tri-, Tetra-, and Polyketones 138 Diketones with Substituents Containing Additional Donor Atoms 139 Diketones with Substituents Containing Metallic or Metalloid Atoms 141 Acylpyrazolones and Analogue beta-Diketones with a Heterocycle Fused to the Chelating Ring 141 References 144 1.7 Phenylcyanamide Ligands 148 Introduction 148 Synthesis of Phenylcyanamide Derivatives 148 Neutral Phenylcyanamides (pcydH) 148 Anionic Phenylcyanamides (pcyd-) 149 Physical Properties of Phenylcyanamides 149 Coordination Chemistry of Phenylcyanamides 150 Coordination Geometry 150 Complex Synthesis 151 Ruthenium Complexes 151 Cobalt Complexes 152 Nickel, Palladium, and Platinum Complexes 153 Copper, Silver, and Gold Complexes 153 Summary 154 References 155 1.8 Benzimidazole Ligands 156 Introduction 156 Synthetic Methods for Benzimidazole Derivatives 156 Design of Imidazole/Benzimidazole Ligands 158 Modular Approach 158 Chelate Ligands Composed of a Combination of Bidentate Ligands 159 Chelate Ligands Composed of a Combination of Tridentate Ligands 160 Chelate Ligands Composed of Miscellaneous Combinations 161 Chemical Functions of Coordination Compounds with Imidazole/Benzimidazole Ligands 162 References 164 1.9 Polyatomic Bridging Ligands 166 Scope and Limitations 166 Introduction to Bridging Ligands 167 Monodentate Bridging Ligands 168 Introduction 168 Cyanide 168 Diazines and Polyazines 168 Fused Pyrazine Ring Systems 169 Linked Pyridines 169 Bidentate Bridging Ligands 171 Introduction 171 Bridging Ligands with Donor Atoms Outside the Ring 171 Bridging Ligands with Multiple Donor Atoms in a Ring 172 Bridging Ligands with Pyridine Subunits 173 Conjugated spacers 174 Nonconjugated spacers 175 Bridging Ligands with Phenanthroline Subunits 175 Fused ring systems 176 Linked phenanthrolines 177 Tridentate Bridging Ligands 178 Introduction 178 Pyridine-based Bridging Ligands 178 Phenanthroline-based Bridging Ligands 179 Other Bridging Ligands 179 Mixed-denticity Ligands 180 Linked Bridging Ligands 180 Orthometallated and Interlocked Bridging Ligands 181 Porphyrin-containing Bridging Ligands 181 Cavity Bridging Ligands 182 References 184 1.10 Polypyrazolylborate and Scorpionate Ligands 189 Introduction 189 Polypyrazolylborate or Scorpionate Ligands 191 Abbreviation System 191 Preparation of Poly(pyrazolyl)borates 191 Bpx Ligands 193 Specific Bpx Ligands 193 Tpx Ligands 211 Regiochemistry in ligand synthesis 211 Steric effects 212 Electronic effects 213 Coordination Modes 213 Soft S-Donor Scorpionates 214 Hydrobis(mercaptoimidazolyl)Borates (Bmx) 215 Hydrotris(mercaptoimidazolyl)Borates (Tm) 216 Other S3-donor Scorpionates 217 Poly(Imidazolyl)Borates 217 Poly-(triazolyl)- (HnB(tz)4-n), -(tetrazolyl)-borates (HnB(tet)4-n) 218 Poly(benzotriazolyl)Borates (HnB(Btz)4-n) 219 Poly(Pyrazolyl)Alkanes 220 Bis(pyrazolyl)Alkanes 220 Coordination modes of bis(pyrazolyl)alkanes 220 Synthesis of symmetrical bis(pyrazolyl)alkanes 222 Synthesis of unsymmetrical bis(pyrazolyl)alkanes 223 Tris(pyrazolyl)Alkanes 224 Synthesis of tris(pyrazolyl)methanes 225 Unsymmetrical tris(pyrazolyl)methane 227 C-alkylated tris(pyrazolyl)methane 228 Poly(Pyrazolyl)Silanes 229 Tris(Pyrazolyl)Methanesulfonato 230 Heteroscorpionates 231 Poly(Azolyl)-Phosphine, -Phosphinate, Phosphazene and Phosphine-Oxide 232 Bis(azolyl)-metallates 233 References 234 1.11 Higher Denticity Ligands 241 Introduction 241 Amines 242 Substituted Diamines 242 Substituted Piperazines 245 Polyamines 245 Diamine-Diamide Ligands 248 1,3-Diamino-2-propanol Derivatives 249 Ligands Containing Aromatic or Heterocyclic Spacers 249 2,6-Substituted Pyridines 249 Xylyl-based Ligands 250 Multidentate Ligands Containing Pyridazine, Phthalazine, Pyrazolyl, Thiazolyl, Oxadiazolyl, Triazine, and Thiophene Bridges 251 Multidentate Ligands Containing More than Two Pyridine Rings 253 Dithia-Alkane Ligands 254 Polyethyleneglycols and Glymes 254 Tripodal Ligands 256 Tripodal Ligands with Nitrogen as the Bridgehead Atom 256 Tripodal Ligands with Carbon as the Bridgehead Atom 261 Macrocyclic Ligands 262 Crown Ethers 263 Cryptands and Polycyclic Compounds 264 Other Preorganized Macrocycles 264 Switchable and Chromogenic Macrocycles 265 Photoresponsive macrocycles 265 pH-responsive macrocycles 266 Redox-responsive macrocycles 267 Ion-responsive fluorescent macrocycles 267 Chromogenic macrocycles 267 Siderophore-type Macrocycles 267 Dendrimeric Ligands 268 Polycarboxylic Acids 270 References 276 1.12 Phosphorus Ligands 282 Introduction 283 Synthesis of Phosphorus-Based Compounds 283 Halophosphines 283 Synthetic routes 283 Physical properties 285 Reactions of halophosphines 285 Primary Phosphines 285 By reduction 285 Using metal phosphides 287 Miscellaneous methods 287 Physical properties 288 Reactions of primary phosphines 288 Coordination chemistry of primary phosphines 288 Secondary Phosphines 288 By reduction 289 Using metal phosphides 289 By P-H addition reaction 290 Miscellaneous methods 290 Physical properties 290 Reactions of secondary phosphines 290 Coordination chemistry of secondary phosphines 291 Catalytic applications of metal complexes with secondary phosphines 291 Tertiary Phosphines 291 Using Grignard reagents 292 Using organolithium reagents 292 Using other organometallics 292 Alkali-metal derivatives 293 Reduction methods 294 Reduction of phosphine oxides 294 Reduction of phosphonium salts 294 Hydrophosphinations 294 Metal-catalyzed phosphinations 295 Miscellaneous methods 295 From elemental phosphorus 295 From polyphosphines 295 Heteroaryltrimethylsilanes 296 Physical properties 296 Coordination chemistry of tertiary phosphines 296 Catalytic applications of metal complexes with tertiary phosphines 296 Unsymmetrical Tertiary Phosphines 296 Preparation by classic methods 296 Miscellaneous methods 297 Functionalized Tertiary Phosphines 297 Ditertiary Phosphines 299 Polydentate Tertiary Phosphines 301 Water-soluble Tertiary Phosphines 303 Synthetic routes to water-soluble tertiary phosphines 303 Coordination chemistry of water-soluble tertiary phosphines 305 Catalytic applications of metal complexes with water-soluble tertiary phosphines 305 Fluorinated Tertiary Phosphines 305 Synthetic routes to fluorinated tertiary phosphines 305 Coordination chemistry of fluorinated tertiary phosphines and catalytic applications 306 Tertiary Phosphine Oxides 307 Synthesis of tertiary phosphine oxides 307 Properties of tertiary phosphine oxides 308 Coordination chemistry and catalytic uses 309 Chiral Phosphorus-based Ligands 309 Synthetic routes 309 Coordination chemistry and catalytic applications of metal complexes with chiral tertiary phosphines 311 Phosphinites, Phosphonites, and Phosphites 311 Synthesis of phosphinites, phosphonites, and phosphites 311 Coordination chemistry 314 Catalytic chemistry 315 (Phosphino)amines 315 By aminolysis reactions 315 From the lithium amide 317 From silylated compounds 317 By aminolysis with (dialkylamino)phosphines 317 Coordination chemistry of (phosphino)amines 317 Catalytic applications of metal complexes with (phosphino)amines 318 Conclusions and Outlook 318 References 318 1.13 Phosphorus Tripodal Ligands 326 Introduction 326 Tripod Ligands with a Trimethylene-Methane Backbone 327 Tripod Ligands with Three Equal Phosphane Donors 327 Tripod Ligands with Three Different Phosphane Donors 328 Tripod Ligands with Chiral Phosphane Donors 330 Tripod Ligands Containing Two Potentially Different Phosphane Donors 331 Tripod Ligands Containing One Phosphane Donor 333 Tripod Ligands Containing RCp Donor Groups 334 Tripod Ligands Based on a Central Carbon with Different Types of Linking Groups 336 Tripod Ligands with One Oxo Bridging Group 336 Tripod Ligands with Different Types of Linker and Donor Groups 336 Tripod Ligands with a Phosphane Donor Bonded to the Central Carbon 339 Tripod Ligands Based on a Central Heteroatom 341 Tripod Ligands with a Neopentane-like Scaffolding 341 Tripod Ligands with a Central Silicon 342 Tripod Ligands with a Central Nitrogen 342 Tripod Ligands with a Central Phosphorus 343 Tripod Ligands Based on Miscellaneous Scaffoldings 345 Tripod Ligands Based on Tartaric Acid 347 Tripod Ligands Based on Calixarenes 347 Tripod Ligands Based on Sesquisilanes 347 Heterocycles as Tripod Ligands 347 Summary 349 References 349 1.14 Dichalcogenoimidodiphosph(in)ate Ligands 352 Introduction 352 Synthesis 353 Preparative Reactions 353 Oxidation of bis(phosphino)amines - method A 353 Oxidation of bis(phosphino)amines - method B 354 Coupling of Phosphoryl or Phosphinyl Amides with Phosphoryl or Phosphinyl Halides 354 Organolithium reagents 354 Sodium hydride 354 Alcoholysis of bis(dichlorophosphoryl)amide (tetrachlorodioxodiphosphazane) 355 Other Formation Reactions 356 Thermal condensation of phosphinyl amides 356 Hydrolysis of diphosphazene chlorides 356 Hydrolysis of other functional diphosphazene derivatives 356 Alcoholysis of trichlorophosphazo derivatives, followed by partial acid splitting of R1O groups 357 Coupling of phosphoryl azides with phosphites, followed by acid splitting of OR1 groups 357 Hydrolysis or alcoholysis of N-silylated imidodiphosphoryl derivatives 357 Splitting of OR1 groups from phosphate esters with sodium amide 357 In situ formation of imidodiphosphinato ligands 357 Acidity And Preparation Of Alkali Metal And Other Salts 358 Spectroscopic And Structural Characterization 363 Coordination Patterns 364 Metal Complexes 370 Conclusions 371 References 371 1.15 1,1-Dithiolato Ligands 377 Introduction 377 Dithiophosphinates, Dithiophosphates, and Dithiophosphonates 378 General 378 Synthesis 378 Dithiophosphinic acids, R2P(S)SH 378 Dithiophosphoric acids (diesters) (RO)2P(S)SH 379 Dithiophosphonic acids, R1(R1O)P(S)SH 379 Coordination patterns 379 Metal complexes 380 Dithiophosphinates 380 Dithiophosphates 382 Dithiophosphonates 383 Dithioarsinates 385 General 385 Synthesis 385 Coordination patterns 385 Metal complexes 385 Dithiocarbonates (Xanthates) 387 General 387 Synthesis 387 Coordination patterns 389 Metal complexes 390 Dithiocarboxylates 391 General 391 Synthesis 392 Coordination patterns 392 Metal complexes 393 Dithiocarbamates 395 General 395 Synthesis 395 Coordination patterns 395 Metal complexes 395 References 397 1.16 Acyclic Arsine, Stibine, and Bismuthine Ligands 405 Introduction 405 Arsine Synthesis 406 Stibine Synthesis 407 Bismuthine Synthesis 410 Arsines, Stibines, and Bismuthines as Ligands 411 Bonding 411 Coordination modes 413 References 415 1.17 Acyclic Thio-, Seleno-, and Telluroether Ligands 418 Introduction 418 Synthesis of Acyclic Thio-, Seleno-, and Telluroether Ligands 418 Thioethers 418 Selenoethers 419 Telluroethers 420 Acyclic Thio-, Seleno-, and Telluroethers as Ligands 422 Bonding 422 Coordination Modes and Properties 423 References 423 1.18 Macrocyclic Thio-, Seleno-, and Telluroether Ligands 426 Introduction 426 Thioether Macrocycles 427 Coordination Chemistry and Properties 428 Selenoether Macrocycles 430 Telluroether Macrocycles 433 Coordination Chemistry and Properties 435 Abbreviations 435 References 436 1.19 Acyclic and Macrocyclic Schiff Base Ligands 438 Introduction 438 General Properties 439 General Synthetic Method 439 General Spectroscopic Properties 440 Tautomerism 440 Intramolecular Nucleophilic Attack 441 Monodentate Schiff Bases 441 Bidentate Schiff Bases 442 N,N and N,O Donors 442 N,S(Se) Donors 443 N,P Donors 444 Tridentate Schiff Bases 444 N,O Donors 444 Other Donors 445 Tetradentate Schiff Bases 447 N,O and N,N Donors 447 Asymmetrical 447 Symmetrical 449 N,S, N,O,S and other Donors 452 Chiral Tetradentate Schiff Bases 453 Equilibrium Studies 454 Pentadentate Schiff Bases 455 Compartmental Acyclic Schiff Bases 455 Phenol-based Derivatives 456 Di- and Triketone Derivatives 458 End-off Ligands 459 Polypodal Ligands 460 Macrocyclic Schiff Bases 462 Compartmental Macrocycles 464 Noncompartmental Macrocycles 466 Bibracchial Macrocycles 467 Ring Contraction and Expansion 468 Acknowledgement 470 References 470 1.20 N Macrocyclic Ligands 474 Introduction and Scope 474 Cyclic Secondary Amines 476 Azamacrocycles with Imine Functions 477 Ketone and beta-enone-Amine Reactions 478 2,6-Dicarbonyl Pyridine-Amine Reactions 479 Aromatic Aldehyde-Amine Reactions 479 beta-Keto Imine-Amine Reactions, Cyclidenes 479 Alpha-Dicarbonyl-Amine Reactions 480 Beta-Dicarbonyl-Amine Reactions 480 Compartmental Macrocycles 481 Azamacrocycles with Amide or Amidate Functions 481 Macrocycles Formed by Mannich Condensations, Azacyclams 484 Azamacrocycles with C-Substituents 485 Functionalized C-substituents 485 Substituents Introduced via Amide Formation 486 Substitution of 1,3-diimine or Iminato Six-membered Chelate Rings 486 Nitro- and Amine-substituents 486 Nitromethyl and Aminomethyl Substituents 487 Carboxyl Substituents 488 2-Pyridyl Substituents 489 Hydroxymethyl Substituents 489 C-pendants that Coordinate Exocyclic Cations 489 Azamacrocycles with N-Substituents 490 Unfunctionalized Substituents 491 Carboxyalkyl Substituents 491 Carbamoylmethyl Substituents 492 Hydroxyalkyl Substituents 492 Nitrile Substituents 492 Omega-Aminoalkyl Substituents 492 Pyridylmethyl Substituents 493 N-pendants that Coordinate an Exocyclic Cation 493 Other N-substituents 493 Bi- and Tricyclic Azamacrocycles 494 Linked Azamacrocycles 495 Cyclic Amines with a Shared C-C Bond 495 Spiro-azamacrocycles 495 C-C ́-linked Bisazamacrocycles 496 N-X-N ́ Linked Bisazamacrocycles 496 Conclusions 498 References 498 1.21 Macrocyclic Phosphine and Arsine Ligands 502 Introduction 502 Phosphine Macrocycles 502 Arsine Macrocycles 509 References 511 1.22 Calixarenes 512 Introduction 512 Unsubstituted Calixarenes 513 Aryloxides 515 Substituted Calixarenes 516 Oxygen and Nitrogen Donor Atoms 516 Sulfur and Phosphorus Donor Atoms 517 Calixcrowns 517 References 517 1.23 Porphyrins 519 Introduction 519 Strategic Considerations in Porphyrin Synthesis 520 Porphyrin Syntheses using a Monopyrrole Tetramerization Approach 521 2,3,7,8,12,13,17,18-Octaethylporphyrin (H2OEP (1)) 521 5,10,15,20-Tetraphenylporphyrin (H2TPP (2)) 525 Porphyrin Syntheses using Reactions of Dipyrroles 526 Using Dipyrromethenes 526 Syntheses of dipyrromethenes 526 Transformation of dipyrromethenes into porphyrins 526 Using Dipyrromethanes 527 Syntheses of dipyrromethanes 527 Transformation of dipyrromethanes into porphyrins 528 5,15-Diaryl and 5,15-Dialkylporphyrins 531 Acknowledgement 532 References 532 1.24 Phthalocyanines 533 Introduction 533 General Synthetic Considerations 534 Substituted Phthalocyanine Ligands 535 The Preparation of Substituted Derivatives by the Reaction of Preformed Pcs 536 Nonuniformly Substituted Pcs 536 Azaphthalocyanines 537 Tetraazaporphyrins 538 Extended Phthalocyanines 538 References 539 Section II - Synthesis, Purification, and Characterization of Coordination Compounds 541 1.25 Metal Aqua Ions 541 Introduction 542 Representative Nature of Aqua Ions 542 Geometry of Aqua Ligands 542 Survey of Groups in the Periodic Table 543 Group 1: Li+(aq), Na+(aq), K+(aq), Rb+(aq),Cs+(aq) 543 Group 2: Be2+(aq), Mg2+(aq), Ca2+(aq), Sr2+(aq), Ba2+(aq), Ra2+(aq) 544 Group 3: Scandium, Yttrium, the Lanthanides, and Actinides 544 Group 4: Titanium, Zirconium, and Hafnium 546 Group 5: Vanadium, Niobium, and Tantalum 548 Group 6: Chromium, Molybdenum, and Tungsten 550 Group 7: Manganese, Technetium, and Rhenium 553 Group 8: Iron, Ruthenium, and Osmium 555 Group 9: Cobalt, Rhodium, and Iridium 556 Group 10: Nickel, Palladium, and Platinum 559 Group 11: Copper, Silver, and Gold 559 Group 12: Zinc, Cadmium, and Mercury 560 Group 13: Boron, Aluminum, Gallium, Indium, and Thallium 561 Group 14: Germanium, Tin, and Lead 562 Group 15: Arsenic, Antimony, and Bismuth 563 Group 16: Sulfur, Selenium, and Tellurium 563 Ligand Substitution Reactions 563 Range of Labilities of Aqua Metal Ions 563 Formation of Metal Complexes 565 Classification of Mechanisms 566 Volume of Activation 567 Substitution of Main Group Metal Ions 569 Group 1 Li+, Na+, K+, Rb+, Cs+ 569 Group 2: Be2+, Mg2+ 569 Group 3: Al3+, Ga3+, In3+ 570 Substitution of Transition Metal Aqua Ions 570 Six-coordination Divalent Transition Metal Aqua Ions 570 Six-coordinate Trivalent Transition Metal Aqua Ions 573 Divalent Square-Planar Transition Metal Ions 574 Transition Metal Oxo/Aqua Ions 574 Substitution of Lanthanide Metal Ions 575 Trivalent Lanthanide Metal Ions 575 Divalent Lanthanide Metal Aqua Ions 577 References 577 1.26 Solvents and Ionic Liquids 582 Introduction 582 Solvent Properties 582 Assessment of Solvent Polarity 583 Donor number 583 Acceptor number 584 ET(30) and ETN parameters 584 Solvent Classification 584 Classification based on chemical constitution 584 Classification based on physical constants 585 Other classification 585 Effect of Solvent on Reactions 586 Ionic Solvents 586 The Cations 587 The Anions 588 Chlorometalates 588 BF4- or PF6- containing ionic liquids 588 Solvent Properties of Ionic Liquids 589 Perfluorinated Solvents 590 Supercritical Fluids 590 The Challenge for the Future 590 References 590 1.27 Chromatographic Methods 592 Choosing the "Right" Chromatography 592 Scope and Review of Other Sources 593 General Separation Techniques 593 Separations of Chiral Complexes and Isomers 594 Capillary and Capillary Zone Electrophoresis of Complexes 595 Electrospray Mass Spectral Detection of Metal Complexes 596 Size-exclusion Chromatography (SEC) for Metal Complexes 596 IMAC Separations via Inorganic Complexes 597 Immobilized Metal Complexes for Organic Separations (IMCOS) 598 Computer-Aided Chromatography Involving Metal Complexes 599 References 601 1.28 Crystal Growth Methods 603 Introduction 603 Solvent Evaporation 604 Cooling 604 Solvent Liquid Diffusion 605 Solvent Vapor Diffusion 605 Sublimation 605 Crystal Growth from the Melt 606 Slow Diffusion of Reactants 606 Other Approaches to Obtaining Better Crystals 607 Section III - Reactions of Coordinated Ligands 608 1.29 Ligand Reactivity: General Introduction 608 Introduction 608 Factors Affecting Ligand Reactivity 609 Electron-acceptor/donor Properties of the Metal Center 609 Electron-donor/acceptor Properties of the Ligands 610 Effect of Co-ligands 611 Reactions Occurring Upon Coordination 611 Acid-Base and Related Reactions 611 Internal Redox Reactions between Ligand and Metal Center 612 Ligand Coupling 612 Template Synthesis 612 Metal-induced Rearrangements 613 Stabilization of Unstable Species and Protection of Functional Groups by Metal Centers 613 Summary and Conclusions 613 References 614 1.30 Reactivity and Structure of Complexes of Small Molecules: Carbon Dioxide 618 Introduction 618 Carbon Dioxide as a Ligand 618 Bonding and Structural Types 618 Synthesis 620 Infrared Spectral Characteristics 620 Characteristic Reactions 621 Decarboxylation 621 Oxygen Transfer 621 Reactions with Electrophiles 621 Insertion of Co2 In Metal-X Bonds (X=C, H, O, N, Si, P, Metal) 622 Oxidative Coupling 622 Catalytic Reduction of Co2 623 Summary and Future Directions 624 References 624 1.31 Reactivity and Structure of Complexes of Small Molecules: Nitric and Nitrous Oxide 626 Structure and Bonding 626 General Properties of NO, Bonding Models, and the Enemark-Feltham Formalism 626 Solid-state Structures of eta1-N-Mononuclear Nitrosyls. CoordinationNumbers: 6, 5, 4, and Others. Spectroscopic Characteriz 628 Coordination number 6 628 Coordination number 5 633 Coordination number 4 and others 635 Polynitrosyls, Bridging Nitrosyls, and Clusters 635 eta1-ON (Isonitrosyls) and eta2-NO Complexes 635 N2O Complexes 636 Synthesis and Reactivity of No and N2o Complexes 638 Reactions of NO 638 Synthesis 638 Formation and dissociation reactions of NO 640 Nucleophilic additions to bound NO 640 Reduction of bound NO: chemistry and electrochemistry 641 Reductive nitrosylation 641 Electrophilic reactions 642 Disproportionation of metal-bound NO 642 Nitrosyl transfer 642 Reactions of N2O 642 Synthesis of N2O complexes 642 Reduction of N2O involving O-atom transfer 643 N-N bond cleavage of N2O 643 N2O formation involving N-atom transfer 643 N2O from reductive coupling of NO 643 Catalyzed disproportionation of NO in basic medium 643 Electroreduction catalyzed by transition-metal complexes 644 Conclusions and Outlook 644 References 644 1.32 Reactivity and Structure of Complexes of Small Molecules: Dioxygen 647 Introduction 647 First-Row Transition Metals 647 Second- and Third-Row Transition Metals 650 References 651 1.33 Reactivity of Coordinated Oximes 652 Introduction 652 Reactions with Preservation of the {Cno} Fragment 652 Reactions Centered at the O-atom 653 Reactions Centered at the N- or the C-atom 654 Reactions with Rupture of the {Cno} Fragment 656 Reactions with N-O Bond Cleavage 656 Reactions with Complete N=C Bond Cleavage 657 References 657 1.34 Reactivity of Coordinated Nitriles 659 Introduction 659 Nucleophilic Additions 660 Reactions with Aprotic Nucleophiles and Subsequent Electrophilic Additions 660 Reactions with protic Nucleophiles 663 Formation of C-O bonds 663 Water and alcohols 663 (NOH) nucleophiles: oximes and hydroxylamines 667 Formation of C-N bonds 667 Formation of C-P, C-S, and C-C bonds 671 Cycloadditions 671 Electrophilic Additions 673 Final Remarks 677 References 677 Section IV - Stereochemistry, Structure, and Crystal Engineering 681 1.35 Lone Pair Effects and Stereochemistry 681 Introduction 681 Theoretical Background 681 Results and Applications 684 The Hardness Rule 684 The Energetic Origin of the Lone-pair Effect 685 conclusions and Summary 687 References 687 1.36 Outer Sphere Coordination Chemistry 688 Introduction 688 Solute-Solvent Interactions (SSI) 688 Higher Sphere Ligand Fields (HSLF) 689 Symmetry Effects by the Second Coordination Sphere 689 Bond Strength and Covalency Effects Induced by the Second Coordination Sphere 691 The Stabilization of High Oxidation States of the Late 3d-Metals by Second Coordination Sphere Effects 693 Bonding Anisotropy by Orbital Phase Coupling 696 Summary 696 References 696 1.37 Solid State, Crystal Engineering and Hydrogen Bonds 698 Introduction and Scope 698 Strategies for Supramolecular Synthesis 699 Coordination Polymers 699 The Hydrogen Bond 699 1D Architectures 700 1D Assemblies Based on Silver(I) Complexes 700 Linear Networks Containing other Transition-metal Ions 701 Supramolecular Chains Incorporating Macrocycles 701 Halometallates as Hydrogen-bond Acceptors 701 2D Architectures 702 2D Assemblies Based on Platinum(II) Complexes 702 Layered Networks with other Transition-metal Ions 702 Metalloporphyrins as Supramolecular Building Blocks 703 3D Architectures 704 Combining Coordination Polymers and Hydrogen Bonds 704 References 706 Section V - New Synthetic Methods 708 1.38 Biphasic Synthesis 708 New Chemical Protocols 708 The Approaches to Biphasic Synthesis 708 The Traditional Biphasic Approach 709 Temperature Dependent Solvent Systems 709 Single to Two-phase Systems 709 Other Systems 709 Solvent Combinations 709 Aqueous-Organic 710 Phase transfer catalysis 710 Supported aqueous phase catalysis 710 Ionic Liquid-Organic 710 Ionic Liquid-Aqueous 712 Fluorous-Organic 713 Other Solvent Combinations 713 Triphasic Systems 713 Solid-Liquid Biphasic Catalysis 713 Biological Relevance 713 References 714 1.39 Solid State Methods, Hydrothermal 715 Introduction 715 Hydrothermal Synthesis of Organic-Inorganic Hybrid Materials: General Considerations 715 Typical Reaction Conditions 716 The Organic Component 716 Molecular Clusters 718 Metal Organophosphonates 718 Inorganic Oxides Incorporating Organoimine Ligands 720 Bimetallic Oxide Networks 722 Metal-Halide and -Pseudohalide Materials 725 Conclusions 726 References 726 1.40 Sol-Gel 728 Introduction 728 Hydrolysis and Condensation 730 Control of Morphology 731 Metal Alkoxide Precursors 732 Modifiers 732 Multinuclear Alkoxide Precursors: Homonuclear 733 Multinuclear Alkoxide Precursors: Heteronuclear 734 Non-hydrolytic Condensation of Alkoxides 735 Thiols and Non-oxide Gels 735 Organic-Inorganic Hybrid Materials 735 Alkyltrialkoxysilanes and Silasesquioxanes 736 Doping with Dyes 737 Doping with Biomolecules 737 Doping with Polymers 737 Templating of Sol-Gel Materials 738 Aqueous Colloidal Precursors: Condensation 739 Examples of Sol-Gel Syntheses In Catalysis,Electroceramics, Electrochromics, and Biomaterials 742 Conclusions 743 References 743 1.41 Sonochemistry 748 Introduction 748 Acoustic Cavitation 749 Microjet Formation During Cavitation at Liquid-Solid Interfaces 750 Sonoluminescence 751 Types of Sonoluminescence 751 Spectroscopic Probes of Cavitation Conditions 751 Sonochemistry 752 Homogeneous Sonochemistry: Bond Breaking and Radical Formation 752 Applications of Sonochemistry to Materials Synthesis 753 Heterogeneous Sonochemistry: Reactions of Solids with Liquids 754 Conclusions 755 References 756 1.42 Microwave Heating 757 Introduction: Microwaves in Condensed Phase Chemistry 757 Mechanisms of Microwave Heating in Condensed Matter 757 Comparison of Microwave and Conventional Heating 758 Microwave-specific Effects 759 Nonthermal Effects 759 Microwave Equipment 759 Microwave Applicators 759 Reaction Vessels 760 Temperature Measurement 760 Specific Applications to Coordination Chemistry 760 Conclusions 760 References 761 1.43 Assemblies and Self-assembly 762 Introduction 762 Types of Self-Assem V. 1. Fundamentals : Ligands, Complexes, Synthesis, Purification, And Structure -- V. 2. Fundamentals : Physical Methods, Theoretical Analysis, And Case Studies -- V. 3. Coordination Chemistry Of The S, P, And F Metals -- V. 4. Transition Metal Groups 3-6 -- V. 5. Transition Metal Groups 7 And 8 -- V. 6. Transition Metal Groups 9-12 -- V. 7. From The Molecular To The Nanoscale : Synthesis, Structure, And Properties -- V. 8. Bio-coordination Chemistry -- V. 9. Applications Of Coordination Chemistry -- V. 10. Cumulative Subject Index. Editors-in-chief, Jon A. Mccleverty, Thomas J. Meyer. Includes Bibliographical References And Indexes.