Comprehensive Coordination Chemistry II - From Biology to Nanotechnology 2 ed. in 10 Vol.Set Volume 06 - Transition Metal Groups 9-12

McCleverty J.A. (ed.) Comprehensive Coordination Chemistry II - From Biology to Nanotechnology 2 ed. in 10 Vol.Set Volume 06 - Transition Metal Groups 9-12 2003 [pdf 1295sc 1292+1c. 17.91mb]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. Cover Page 1 Introduction to Volume 6 2 COMPREHENSIVE COORDINATION CHEMISTRY II 4 Volumes 5 Info on Volume 6 6 Volume 6 -1 6.1 Cobalt 7 Introduction 8 Introductory Remarks and General Scope 8 Synthesis, Reactivity, and Structure 10 Metal Complexes 11 Co-I, Co0, and CoI 12 Carbon 12 Cyanides 12 Carbonyls 12 Alkyls and aryls 14 Other carbon-bonded ligands 14 Silicon 15 Nitrogen 15 Amines 15 Pyridine and oligopyridines 15 Porphyrins 16 Pyrazole and related ligands 16 Imines 16 Dinitrogen 18 Nitrosyl 18 Nitriles and azides 19 Phosphorus 19 Monodentate phosphines 19 Multidentate phosphines 20 Arsenic 21 Oxygen 22 Sulfur 22 Sulfides 22 Thioethers 22 Thiolates 22 Thiocarbamates 22 Thioureas 23 Halogens 23 Hydrogen 23 Hydrides 23 Dihydrogen 24 CoII 25 Carbon 25 Cyanides 25 Carbonyls 25 Carbon dioxide 26 Alkyls and aryls 26 Nitrogen 27 Amines 27 Pyridine and oligopyridines 29 Porphyrins 33 Imidazole, pyrazole, and related ligands 34 Imines and oximes 37 Amides 43 Nitrosyl 43 Nitriles, azide, cyanates, and thiocyanates 44 Phosphorus 45 Monodentate phosphines 45 Multidentate phosphines 45 Arsenic 47 Monodentate and multidentate arsines 47 Oxygen 48 Aqua, hydroxo, and oxo 48 Dioxygen 49 Neutral oxygen donors 50 Alkoxides and aryloxides 50 Ethers 50 Ketones and esters 51 Amides 51 Carbonates, carbamates, and carboxylates 51 Oxoanions of N, S, P, and the halogens 53 Mixed O, N Donors 55 Sulfur 55 Sulfides 55 Thioethers 56 Thiolates 57 Dithioacids and thiosemicarbazones 58 Thioureas 59 Mixed S, N and S, O ligands 59 Halogens 60 Halides 60 CoIII 61 Carbon 61 Cyanides 61 Carbonyls 61 Alkyls and aryls 62 Silicon and tin 64 Nitrogen 64 Amines 64 Pyridine and oligopyridines 73 Porphyrins, corrinoids, and polypyrroles 74 Imidazole, pyrazole, and related ligands 76 Imines 76 Oximes 79 Amides 79 Nitrosyl 83 Nitriles, azides, isocyanides, cyanates, and thiocyanates 83 Phosphorus 85 Arsenic 87 Monoarsines and multidentate arsines 87 Oxygen 88 Aqua, hydroxo, and oxo 88 Dioxygen, superoxide, and peroxide 89 Neutral oxygen donor ligands 91 Alkyl peroxides 91 Ketones and esters 92 Carbonates, carbamates, and carboxylates 92 Oxoanions of N, S, P, and the halogens 93 Mixed O, N ligands 95 Sulfur and selenium 96 Sulfides and selenides 96 Thioethers and selenoethers 97 Thiolates 98 Thiocarbamates 99 Thiosemicarbazones 100 Thioureas and selenoureas 101 Mixed donor sulfur and selenium ligands 101 Halogens 103 Halides 103 Hydrogen 104 Hydrides 104 CoIV and CoV 104 Carbon 104 Nitrogen 104 Oxygen 105 Biological Chemistry of Cobalt 105 Metalloproteins and Cofactors 105 Cobalamins (B12) 105 B12 cofactors 107 B12 model complexes 109 Non-corrin proteins 112 Native cobalt-dependent proteins 112 Cobalt-modified proteins 113 Biomimetic chemistry 115 Dioxgen binding 115 Polyphosphate and phosphate ester hydrolysis 117 DNA binding, intercalation, and scission 118 Biological electron transfer 120 Medicinal chemistry 120 Industrial and Analytical Applications of Cobalt Complexes 120 Organic Transformations 120 Oxidations 121 Carbonylation and formylation 122 Cycloadditions and asymmetric synthesis 122 Other catalytic reactions 124 Polymerization 124 Electrocatalysis and Analytical Sensors 125 Environmental 126 Technology 126 Conclusion 128 References 128 6.2 Iridium 152 Introduction 154 Iridium(VI) 154 Iridium(V) 154 Boron Ligands 155 Silyl and Stannyl Ligands 155 Nitrogen, Phosphorus, Arsine, and Stibine Ligands 155 Oxygen Ligands 156 Halide Ligands 156 Hydrogen Ligands 156 Mixed-donor-atom Ligands 157 C/Si 157 Iridium(IV) 158 Boron Ligands 158 Nitrogen, Phosphorus, Arsine, Stibine, Sulfur, Selenium, and Tellurium Ligands 158 Oxygen Ligands 160 Iridium(III) 161 Mercury Ligands 161 Boron Ligands 161 Carbon Ligands 161 Silicon Ligands 162 Germanium Ligands 164 Tin Ligands 164 Nitrogen Ligands 164 Ammine 164 Nitrosyl 166 Nitrile 167 Nitride 167 Urea 167 Nitrite 167 Cyanide 168 Pyridine 168 Phthalimide 168 Imidazole 168 Pyrazole 169 Chelate-ethylenediamine 169 alpha-diimine 170 Binuclear complexes 172 N3 ligands 173 N4 ligands 174 Phosphorus Ligands 175 Monodentate ligands 175 Bidentate ligands 177 Tridentate ligands 179 Arsine and antimony ligands 179 Oxygen Ligands 179 Monodentate ligands 179 Bidentate ligands 180 Tridentate ligands 181 Trinuclear complexes 181 Sulfur and Selenium Ligands 181 Monodentate ligands 181 Bidentate ligands 182 Binuclear complexes 183 Tridentate ligands 183 Halide ligands 183 Hydrogen Ligands 183 Mixed-donor-atom Ligands 186 C/N 186 C/P 189 C/O 189 Si/N 190 Si/P 190 N/P 191 N/O 191 N/S 192 P/O 194 P/S 195 P/Br 195 O/S 195 Multidentate ligands 196 Biological Complexes 199 Catalytic Complexes 201 Iridium(II) 202 Carbon Ligands 202 Tin Ligands 202 Nitrogen Ligands 202 Phosphorus Ligands 205 Oxygen Ligands 205 Sulfur Ligands 205 Halide Ligands 206 Hydrogen Ligands 206 Mixed-donor-atom Ligands 207 C/P 207 N/P 207 N/S 207 Biological Complexes 208 Catalytic Complexes 208 Iridium(I) 208 Carbon Ligands 208 Isocyanide 208 Carbonyl 208 Alkyls and aryls 208 Silicon Ligands 209 Nitrogen Ligands 210 Pyridine 210 Nitriles 210 Nitride 210 Nitrosyl 210 Amides 211 alpha-diimines 211 Pyrazole and derivatives 212 Bis-chelating Ligands 213 Polydentate N-donor ligands 215 Phosphorus Ligands 216 Monodentate Ligands 216 Polydentate ligands 220 Arsine and Stibene Ligands 222 Oxygen Ligands 223 Monodentate Ligands 223 Bidentate ligands 224 Sulfur Ligands 225 Monodentate Ligands 225 Bidentate ligands 225 Tridentate ligands 226 Binuclear complexes 226 Bimetallic complexes 226 Selenium and Tellurium Ligands 226 Halide Ligands 227 Hydrogen Ligands 227 Mixed-donor-atom Ligands 227 C/N 227 C/P 227 Si/P 228 N/P 228 N/O 230 N/S 231 P/O 231 O/S 232 Multidentate ligands 232 Biological complexes 233 Catalytic Complexes 234 Iridium(0) 235 Nitrogen Ligands 235 Phosphorus Ligands 235 Monomeric complexes 235 Dimeric complexes 236 Mixed-donor-atom Ligands 236 C/P 236 N/P 236 Iridium (-I) 236 Phosphorus Ligands 237 Mixed-donor-atom Ligands 237 C/P 237 Abbreviations 237 References 239 6.3 Nickel 252 Introduction 254 Relevance in Bioinorganic Chemistry and Materials Chemistry 254 Nickel in Biology 254 Nickel in Materials Chemistry 256 Complexes of Nickel(III) and Nickel(IV) 257 Introduction 257 Cyano Complexes 257 Complexes with N-donor Ligands 257 Complexes with nonmacrocyclic N-donor ligands 257 Complexes with macrocyclic N-donor ligands 259 Complexes with Ligands Containing Phosphorus, Arsenic, and Antimony 264 Complexes with O-donor Ligands 265 Complexes with Ligands Containing S- and Se- donors 266 Halide Complexes 270 Complexes with Bioligands 271 Complexes with peptides, amino acids, and related ligands 271 Complexes with oximes and related ligands 272 Complexes with porphyrins and related ligands 273 Complexes with Mixed Donor Set Ligands 276 Complexes with mixed {N,O} ligands 276 Complexes with mixed {N,S} ligands 276 Complexes with miscellaneous ligands 278 Complexes Of Nickel(II) 280 Advances in Structural Trends and Spectroscopy of Nickel Complexes 280 General structural features 280 Electronic absorption spectroscopy 282 NMR spectroscopy 282 EPR spectroscopy 283 XAS at the nickel K-edge 284 61Ni Mossbauer spectroscopy 284 Molecular modeling of nickel complexes 284 Carbonyl Complexes 285 Cyano and Other Pseudohalide Complexes 286 Cyano complexes 286 Fulminato, cyanato, thiocyanato, and related pseudohalide complexes 286 Complexes with Nonmacrocyclic Nitrogen Donor Ligands 289 Complexes with monodentate amino, amido, and imido ligands 289 Complexes with chelating amino and amido ligands 291 Complexes with chelating imine ligands 296 Complexes with chelating nitrogen ligands incorporating oximes and related functions 297 Complexes with chelating ligands incorporating N-heterocycles 299 Complexes with polypyrazolylborates and related tripodal ligands 305 Complexes of miscellaneous nitrogen ligands 309 Complexes with Ligands Containing Phosphorus, Arsenic, and Antimony as Donor Atoms 309 Complexes with mono- and oligodentate phosphine ligands 309 Complexes with phosphido and phosphinidene ligands 312 Complexes with mixed donor atoms involving phosphorus 313 Complexes with ligands containing arsenic and antimony 319 Complexes with Oxygen Donor Ligands 319 Complexes with monodentate oxygen ligands and carboxylates 319 Complexes with beta-diketones and related ligands 323 Complexes with deprotonated hydroxamic acids, catechols, and related ligands 324 Complexes with miscellaneous oxygen ligands 326 Complexes with Sulfur-, Selenium-, and Tellurium-containing Ligands 327 Complexes with sulfido and monodentate thiol ligands 327 Complexes with dithiol ligands 329 Complexes with thioether and mixed thioether/thiol ligands 331 Complexes with dithiophosphates and related ligands 334 Complexes with xanthates and related ligands 337 Complexes with dithiocarbamate and related ligands 339 Complexes with thiooxalate and related ligands 340 Complexes with dithioketones and related ligands 340 Complexes with thiourea and related ligands 341 Complexes with dithiolene ligands 342 Complexes with selenium- and tellurium-containing ligands 347 Halide Complexes 349 Mononuclear Complexes with Open-chain Ligands Containing Mixed Donor Atoms 351 Complexes with mixed {N,O} ligands 351 Complexes of Schiff base and related ligands 351 {N,O} edta-type and related polydentate chelating agents 356 Complexes with miscellaneous {N,O} ligands 359 Complexes with mixed {N,S} ligands 359 Thiosemicarbazide, thiosemicarbazones, and related ligands 359 Complexes with mixed amine/thiolate ligands 363 Complexes with mixed amine/thioether ligands 367 Complexes with mixed imine/thiolate and imine/thioether ligands 369 Complexes with mixed {N,O,S} ligands 376 Complexes with Macrocyclic Ligands 378 Complexes with 1,4,7-triazacyclononane-type ligands 378 Sandwich complexes with tacn ligands 378 Complexes of tacn-based ligands with pendent donor side arms 380 Complexes of heteroanalogous tacn-type ligands 382 Complexes with larger macrocyclic nitrogen ligands 384 Synthesis 384 Structures and spectroscopic properties 391 Electrochemical properties91 396 Equilibrium between square planar and octahedral species91 398 Reactions and applications 401 Complexes with larger macrocycles containing mixed donor atoms 405 Complexes with Bioligands 408 Complexes with amino acids and amino acid derivatives 408 Complexes with alpha-amino acids 408 Complexes with hydroxamic and oximic analogues of alpha-amino acids 409 Complexes with peptides 410 Complexes with peptides bearing noncoordinating side chains 410 Complexes with peptides containing side-chain donor systems 412 Complexes with peptides containing histidine 412 Complexes with peptides containing cystein 416 Complexes with porphyrins and related ligands 416 Complexes with core-modified heteroanalogues of porphyrins 422 Complexes with carbohydrates 424 Complexes with nucleosides, nucleotides, and related ligands 425 Ligands for biomimetic and related nickel complexes 426 Di- and Oligonuclear NiII Complexes with Compartmental Dinucleating Ligands 429 Complexes with bis(macrocyclic) ligands 430 Di- and oligonuclear complexes with open-chain alkoxo- or phenolato-based dinucleating ligands 432 Di- and oligonuclear complexes with compartmental macrocycles incorporating O bridges 438 Di- and oligonuclear complexes with thiolate-based dinucleating ligands 442 Model complexes for the urease active site 459 Chain complexes with oligo(pyridylamido) ligands 466 Magnetic Properties of Polynuclear Complexes 468 Complexes with bridging azido ligands 468 Dinuclear complexes 469 Trinuclear, tetranuclear, and high nuclearity complexes 471 One-dimensional uniform systems 474 One-dimensional alternating systems 475 Two-dimensional systems 479 Cyanide-based oligo- and polynuclear complexes 480 Oligonuclear and polymeric complexes with other bridging ligands 480 Complexes with nitronyl nitroxide and verdazyl radical ligands 484 Miscellaneous Complexes of Nickel(II) 485 Complexes with silyl and silylene ligands 485 Hydride complexes 486 Complexes Of Nickel(I) 487 Introduction 487 Complexes with Nitrogen Donor Ligands 487 Complexes with macrocyclic nitrogen donor ligands 487 Complexes with nonmacrocyclic nitrogen donor ligands 491 Complexes with porphyrins and related ligands 492 Complexes with Phosphines and Arsines 494 Complexes with Sulfur- and Selenium-containing Ligands 498 Miscellaneous Complexes of Nickel(I) 501 Complexes Of Nickel(0) 502 Carbonyl and Nitrosyl Complexes 502 Carbonyl complexes 502 Nitrosyl complexes 502 Complexes with CO2, CS2, and related ligands-Electroreduction of CO2 503 Complexes with Nitrogen-containing Ligands 506 Complexes with Dinitrogen and Dioxygen 506 Complexes with Phosphines, Arsines, and Stibines 507 Complexes with mono- and oligodentate phosphines and phosphido ligands 507 Complexes with diphosphenes, phosphabenzene, biphosphinine, and other unsaturated phosphorus donor ligands 511 Complexes with miscellaneous phosphorus donor ligands 514 Complexes with arsenic and antimony donor ligands 514 Miscellaneous Complexes of Nickel(0) 515 Acknowledgement 516 References 516 6.4 Palladium 560 Introduction 561 Scope 561 Previous Reviews 561 Oxidation States Allegedly Higher Than +4 563 Palladium(IV) 564 Carbon 564 Phosphorus 564 Selenium 564 Polynuclear Compounds and Polymers 565 Palladium(III) 565 Mononuclear 565 Various donor atoms 565 Boron 565 Nitrogen 565 Sulfur 566 Halogens 566 Polynuclear Compounds and Polymers 566 Palladium(II) 567 Carbon 567 Silicon and Tin 571 Nitrogen 571 Phosphorus 580 Oxygen 581 Sulfur 584 Selenium and Tellurium 588 Halogens 589 Hydrogen 590 Mixed Donor Atoms 591 Promoters and catalysts for hydrolysis and related reactions 596 Five-coordinate Complexes 601 Polynuclear Compounds 602 Supramolecular assemblies 618 Palladium(I) 643 Carbon 643 Phosphorus 643 Hydrogen 643 Phosphorus 580 Palladium(0) 648 Carbon 648 Nitrogen 648 Phosphorus 649 Hydrogen 650 Mixed Donor Atoms 651 Polynuclear Compounds 652 Nanoparticles 659 Palladium In Negative And Fractional Oxidation States 660 Phosphorus 660 Polynuclear Compounds and Polymers 661 References 661 6.5 Platinum 678 Introduction 679 Platinum(0) 679 Platinum(0) Complexes with Phosphorus Donor Ligands 679 Synthesis 679 Platinum(0) dimers 680 Platinum(0) trimers 680 Hydrides 681 Unusual platinum(0) complexes 681 Unusual phosphine ligands 682 Oxidative addition reactions of platinum(0) complexes 683 Tellurides 683 M-M (M = Si, Ge, Sn) 683 Si-Si 684 M-X (M = Si, Ge, Sn, X = halide) 684 Addition reactions of silanes 684 SiRH3 684 SiR2H2 685 SiR3H 686 Other reactions 686 Reactions with chalcogens 686 Platinum(0) Interactions with Other Metals 687 Spectroscopy 687 Other platinum(0)complexes 687 Platinum(I) 687 Unsupported Dimers 688 Preparations 688 Reactions 689 Hydride Complexes 689 Structures 689 Reactions 689 Phosphine-bridged Dimers 689 Preparation of phosphine-bridged dimers 690 Reactions of phosphine-bridged dimers 691 Dimers Bridged by Unsymmetric Ligands 692 Dimers Bridged by Monodentate Ligands 692 Phosphido-bridged Dimers 693 Electrochemical Reduction and Linear Chain Complexes 693 Platinum(II) 693 Platinum(II) Complexes with Carbonyl and Silicon-donor Ligands 693 Carbonyl ligands 693 Si-Donor ligands 694 Platinum(II) Complexes with Nitrogen-donor Ligands 695 Ammine and alkylamine ligands 695 Amide ligands 700 Amido, imido, and nitrido ligands 701 Nitroso ligands 703 Heterocyclic N-donor ligands 703 Macrocyclic N-donor ligands 708 Amino acid and peptide ligands 709 Platinum(II) Complexes with Phosphorus-, Arsenic-, and Antimony-donor Ligands 711 Mono-, bi-, and tridentate P-donor ligands 711 Macrocyclic P-donor ligands 714 As- and Sb-donor ligands 714 Platinum(II) Complexes with Oxygen-donor Ligands 714 Aqua, hydroxo, and oxo ligands 714 Peroxo ligands 716 Alcohol, alkoxo, and ether ligands 716 Carboxylato and carbonato ligands 719 Platinum(II) Complexes with Sulfur- and Selenium-donor Ligands 720 Sn and Sen ligands 720 Sulfoxide, thiourea, and thiolato ligands 721 Macrocyclic S-donor ligands 722 Platinum(II) Complexes with Hydrido and Dihydrogen Ligands 723 Hydrido ligands 723 Dihydrogen ligands 725 Platinum(II) Complexes with Mixed Donor-atom Ligands 725 Bidentate NO and OS ligands 725 Bidentate P-O, P-S, and P-N ligands 726 Platinum(III) 727 Monomeric Platinum(III) 728 Unbridged Dimers 728 O,O-Bridged Dimers 728 Sulfate and hydrogenphosphate-bridged dimers 728 Pyrophosphito-bridged dimers 729 Acetato-bridged dimers 729 N,S and S,S-bridged Dimers 729 N,O-bridged Dimers 730 Platinum(IV) 730 Five-coordinate Platinum(IV) Complexes 730 Group IV Complexes 731 Group V Complexes 731 Group VI Complexes 732 Am(m)ine Complexes 732 Amino Acid and Peptide Complexes 733 Nucleobase Complexes 733 Macrocyclic and Macrobicyclic Complexes 733 Porphyrin Complexes 734 Reactions of Coordinated Ligands 735 Ligand Exchange Reactions 735 Kinetics and Mechanism of Platinum(IV) Reduction 736 Novel Mechanisms of Platinum(II) Oxidation to Platinum(IV) 737 Hydride Complexes 737 Mixed Oxidation and Mixed Metal Complexes 737 Platinum(0)/Platinum(I) 737 Platinum Blues 738 Linear Chain Complexes 738 Mixed Metal Systems 739 Mixed Oxidation State Clusters 740 Mixed Metal Clusters 740 Acknowledgement 740 References 741 6.6 Copper 751 Introduction: Purpose and Scope 751 Coordination Compounds of Copper(III) 752 Amine Ligands 752 Pyridine-based Ligand 752 Deprotonated Amide Ligands 753 Thiol Ligand 754 Macrocyclic Ligands 754 Coordination Compounds of Copper(II) 756 Nitrogen Donor Ligands 756 Polydentate aliphatic amine ligands 756 Heterocyclic nitrogen donor ligands 756 Imidazole-containing ligands 758 Benzimidazole-containing ligands 764 Pyrazole-containing ligands 771 Pyridine-containing ligands 782 Bipyridine-containing ligands 794 Other heterocycle-containing ligands 797 Oxygen Donor Ligands 804 Phenol-based ligands 804 Alcohol-based ligands 821 Sulfur Donor Ligands 830 Thiol and thioether-containing ligands 830 Amide Ligands 831 Macrocyclic Ligands 844 Ligand-bridged Systems 858 Carbonate ligands 858 Other bridged systems 861 Coordination Compounds of Copper(I) 873 Carbon Donor Ligands 873 Nitrogen Donor Ligands 876 Polydentate aliphatic amine ligands 878 Heterocyclic nitrogen donor ligands 878 Imidazole-containing ligands 878 Benzimidazole-containing ligands 880 Pyrazole-containing ligands 881 Pyridine-containing ligands 885 Bipyridine/phenanthroline-containing ligands 889 Other heterocycle-containing ligands 894 Phosphorus Donor Ligands 894 Oxygen Donor Ligands 895 Sulfur Donor Ligands 899 Thiol- and thioether-containing ligands 899 Macrocyclic Ligands/Cryptands 900 Acknowledgement 903 References 904 6.7 Silver and Gold 915 Introduction 915 Silver 918 Silver(III) 918 Silver(II) 921 Silver(I) 923 Complexes with carbon donor ligands 923 Complexes with nitrogen donor ligands 929 Complexes with monodentate ligands 929 Complexes with polydentate ligands 932 Supramolecular compounds 940 Complexes with phosphorus, arsenic, antimony, or bismuth donor ligands 946 Complexes with monodentate ligands 946 Complexes with polydentate ligands 950 Phosphide- or arsenide-bridged polynuclear complexes 954 Complexes with oxygen donor ligands 956 Complexes with sulfur, selenium, and tellurium donor ligands 963 Thiolates, selenolates, and tellurolate silver(I) complexes 963 Sulfide, selenide, telluride, and polychalcogenide silver(I) complexes 967 Thioether silver(I) complexes 972 Silver(I) complexes with polydentate sulfur ligands 977 Silver(I) complexes with other sulfur donor ligands 981 Complexes with halide and hydride donor ligands 983 Complexes with mixed donor ligands 987 Complexes with silver-metal bonds 992 Gold 994 High Oxidation States 994 Gold(III) Complexes 995 Complexes with carbon donor ligands 995 Complexes with nitrogen donor ligands 999 Complexes with phosphorus, arsenic, antimony, or bismuth donor ligands 1002 Monodentate ligands 1002 Polydentate ligands 1003 Bridging phosphido ligands 1006 Complexes with oxygen donor ligands 1007 Hydroxo, oxo, and alkoxo complexes 1008 Complexes with other oxygen donor ligands 1009 Complexes with sulfur, selenium, or tellurium donor ligands 1010 Complexes with monodentate ligands 1010 Complexes with bidentate ligands 1012 Complexes with halides as donor ligands 1014 Complexes with mixed donor ligands 1014 Gold(II) Complexes 1020 Mononuclear gold(II) complexes 1021 Dinuclear gold(II) complexes 1022 Gold(I) Complexes 1029 Complexes with boron donor ligands 1029 Complexes with carbon donor ligands 1030 Complexes with nitrogen donor ligands 1038 Complexes with phosphorus, arsenic, antimony, or bismuth donor ligands 1043 Phosphide- or arsenide-bridged polynuclear complexes 1043 Complexes with monodentate phosphines, arsines, or stibines 1046 Complexes with polydentate ligands 1051 Complexes with oxygen donor ligands 1060 Complexes with sulfur, selenium, and tellurium donor ligands 1062 Thiolates, selenolates, and tellurolate gold(I) complexes 1062 Sulfide, selenide, telluride, and polychalcogenide gold(I) complexes 1065 Gold(I) complexes with polydentate sulfur ligands 1068 Gold(I) complexes with phosphine sulfide or selenide ligands 1073 Gold(I) complexes with other sulfur donor ligands 1075 Complexes with halide donor ligands 1077 Complexes with hydride donor ligands 1077 Complexes with mixed donor ligands 1079 Gold(I) complexes with AuI-M bonds 1083 Gold Clusters 1087 Homonuclear clusters 1087 Heteronuclear clusters 1090 Gold(0) Complexes 1093 Gold(-I) Compounds 1094 References 1094 6.8 Zinc 1150 Introduction 1151 Coordination Geometry Preferences 1152 Analytical and Physical Techniques for the Study of Zinc Coordination Complexes 1153 Carbon Ligands 1154 Carbonyls 1154 Cyanide and Isocyanide Ligands 1154 Alkyls and Aryls 1155 Nitrogen Ligands 1156 Ammines and Amines 1156 Pyridyl Ligands 1156 Imidazole Ligands 1157 Monoimidazole ligands 1157 Bisimidazole ligands 1157 Trisimidazole and greater 1158 Bridging imidazolates 1159 Pyrazole, Triazole, and other Heterocycle Ligands 1160 Nucleobase and Nucleoside Ligands 1162 Amides, Amidinates, and Guanidinates 1163 Bipyridine and Phenanthroline Ligands 1164 Tripodal Nitrogen Ligands 1165 Tris(pyrazolyl)borate ligands 1165 Other nitrogen donor tripodal ligands 1167 Supramolecular Compounds with Nitrogen Donor Ligands 1169 PhospHorus and Arsenic Ligands 1172 Phosphorus Ligands 1172 Arsenic Ligands 1174 Oxygen Ligands 1175 Hydroxides and Hydrated Species 1175 Alkoxides and Aryloxides 1176 Aldehydes, Ketones, and Ethers 1177 Carboxylates 1179 Basic carboxylates 1179 Mixed-metal carboxylate compounds 1180 Polymeric or framework carboxylate compounds 1180 Other carboxylate type ligands 1181 Phosphate and other Oxyanion Ligands 1183 Phosphates and phosphonate ligands 1183 Other oxyanion ligands 1184 Ester and Phosphate Diester Binding and Hydrolysis 1185 Binding and Formation of Carbonate Species 1187 Acetylacetonate and Related Ligands 1189 Other Oxygen Donor Ligands 1190 Sulfur, Selenium, and Tellurium Ligands 1192 Sulfur Ligands 1192 Thiolates 1192 Thioether ligands and methylation of cysteines 1197 Dithiolates and polysulfides 1198 Dithiocarbamates 1199 Thioformamide, thiocyanate, thiophosphate, and other sulfur donor ligands 1200 Selenium 1201 Selenides 1201 Selenolates 1201 Tellurium 1203 Halide Ligands 1204 Chlorides, Bromides, and Iodides 1204 Reactions and Catalysis 1205 Fluorides 1205 Hydride and Related Ligands 1206 Hydrides 1206 Hydroborate Ligands 1206 Macrocyclic Ligands 1207 Azamacrocycles 1207 Ligands based on triaza crowns 1207 Ligands based on tetraaza crowns 1209 Ligands based on pentaaza crowns and larger 1211 Oxacrowns and Thiacrowns 1212 Mixed Donor Macrocycles 1213 Cryptands and Crossbridged Macrocycles 1216 Compartmental Macrocycles 1217 Porphyrins and Phthalocyanines 1218 Porphyrin-based ligands 1219 Phthalocyanine-based ligands 1223 Ligands with Mixed Donors 1224 Bidentate Mixed Donor Ligands 1224 N/O ligands 1224 N/S ligands 1225 O/S and other ligands 1226 Tridentate Mixed Donor Ligands 1226 Tetradentate Mixed Donor Ligands 1228 Pentadentate and Higher Denticity Mixed Donor Ligands 1230 Liver Alcohol Dehydrogenase Models with Mixed Donor Ligands 1231 Compounds Containing Zinc-Metal Bonds 1232 Applications 1233 Drug Applications 1233 Catalysts 1233 Fluorescent Detection of Zinc in Cellular Systems 1234 Biological Chemistry of Zinc 1236 Zinc in Biological Systems 1236 Other Aspects of Zinc Enzyme and Protein Chemistry 1237 References 1237 6.9 Cadmium and Mercury 1255 Introduction 1255 Bibliography 1255 Scope of the Review 1256 Methods For Studying Formation, Properties, Structures and Bonding In Complex Compounds of Cadmium and Mercury 1256 Experimental Methods 1256 UV/vis spectrometry, thermochemical and electrochemical techniques 1256 NMR spectrometry 1257 NQR spectrometry 1257 Diffraction methods on solids and solutions 1257 X-ray absorption spectrometry 1258 Photoelectron spectrometries 1258 Vibrational spectrometries 1258 Mass spectrometry 1258 Quantum-chemical Calculations 1259 The Occurrence of Cd and Hg 1259 Coordination Compounds of Cadmium and Mercury 1259 Higher Oxidation States of Cd and Hg; Quantum-chemical Studies 1259 The +2 Oxidation States of Cd and Hg 1260 Compounds with donor atom C 1260 Carbonyl complexes 1260 Acetylides 1260 Cyanides 1261 Fulminates 1263 Compounds with donor atoms Si and Ge 1263 Compounds with donor atom N 1264 Amides 1264 Ammine and organic amine complexes 1269 N-coordinating cyanometallates 1277 Compounds with donor atom P 1278 Phosphides 1278 Phosphine complexes 1279 Compounds with donor atoms As and Sb 1280 Frameworks made up of Cd, Hg, and P, As, Sb 1281 Compounds with donor atom O 1281 Cadmium 1281 Mercury 1283 Compounds with donor atoms S, Se, and Te 1284 Cd and Hg chalcogenido complexes 1284 Cd and Hg thiolate and selenolate complexes 1284 Cd and Hg chalcogene clusters 1285 Cd and Hg polychalcogenide complexes 1285 Compounds with halides as donor atoms 1285 Mercury fluoride systems 1285 Cd and Hg halide complexes 1286 Compounds with pseudohalides 1286 Compounds with hydrido ligands 1286 Lower Oxidation States of Cd and Hg 1286 Compounds with formal oxidation states intermediate between +2 and +1 1286 Compounds with triangulo-Hg34+ entities 1286 Mixed-valence compounds with Hg2+ and Hg22+ 1287 Compounds with oxidation state +1 1287 Dimercury(I) compounds 1287 Dicadmium(I) compounds 1287 Subvalent mercury compounds 1288 References 1288 6.10 Appendix to Volume 6 1295 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.