Comprehensive Coordination Chemistry II - From Biology to Nanotechnology 2 ed. in 10 Vol.Set Volume 05 - Transition Metal Groups 7 and 8

McCleverty J.A. (ed.) Comprehensive Coordination Chemistry II - From Biology to Nanotechnology 2 ed. in 10 Vol.Set Volume 05 - Transition Metal Groups 7 and 8 2003 [pdf 849sc 847c. 8.58mb]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 5 2 COMPREHENSIVE COORDINATION CHEMISTRY II 3 Volumes 4 Info on Volume 5 5 Volume 5 -1 5.1 Manganese 6 Introduction 7 Oxidation State VII 8 Oxo and Halide Ligands 8 Nitrogen Donor Ligands 9 Oxidation State VI 9 Oxo Ligands 9 Spectra 11 Nitrogen Donor Ligands 11 Other Complexes 11 Oxidation State V 12 Oxo Ligands 12 Spectra 13 Oxygen Donor Ligands 14 Nitrogen Donor Ligands 14 Nitrogen and Oxygen Donor Ligands 15 Schiff Base Ligands 15 Cyano Ligands 18 Mixed oxidation states MnIV/MnIII 19 Introduction 19 Nitrogen and Oxygen Donor Ligands 21 Dinuclear complexes 22 Mono-mu-oxo bridging 22 Bis-mu-oxo bridging 22 Bis-mu-oxo, mono-mu-carboxylato bridging 23 Mono-mu-oxo, bis-mu-carboxylato bridging 24 Alkoxide and aryloxide bridging 24 Imidazole bridging 24 Tetranuclear clusters 24 Hexanuclear cluster 27 Octanuclear cluster 28 Nonanuclear cluster 28 Decanuclear cluster 29 Oxygen Donor Ligands 29 Dinuclear complexes 29 Tetranuclear clusters 30 Dodecanuclear clusters 33 Hexadecanuclear cluster 35 Higher nuclearity clusters 35 Nitrogen, Oxygen, and Halide Ligands 36 Oxidation State III 39 Introduction 39 Oxygen Donor Ligands 42 Carboxylates 43 Dinuclear complexes 44 Trinuclear clusters 51 Tetranuclear clusters 51 Higher nuclearity clusters 54 Alkoxide and aryloxide ligands 59 Diketones and related ligands 59 Other oxygen ligands 61 Sulfur Donor Ligands 61 Nitrogen Donor Ligands 62 Mixed Donor Polydentate Ligands 63 Bidentate and tridentate 65 Tetradentate 67 Pentadentate 67 Hexadentate 68 Complexes with Macrocylic Ligands 70 Oxidation States IV, V, and VI 70 Nitrogen donor macrocycles 70 Mixed donor macrocycles 71 Oxidation State III 73 Nitrogen donor macrocycles 73 Mixed donor macrocycles 74 Oxidation State II 76 Nitrogen donor macrocycles 76 Phosphorus donor macrocycles 82 Oxygen donor macrocycles 82 Sulfur donor macrocycles 83 Mixed donor macrocycles 83 Oxidation State I 96 Nitrogen donor macrocycles 96 Phosphorus donor macrocycles 96 Sulfur donor macrocycles 96 Bioinorganic Chemistry 96 Introduction 96 Manganese coordination spheres in proteins 97 Acquisition of Mn 97 Enzymes with Mononuclear Active Sites 98 Manganese peroxidase 98 Superoxide dismutase 98 3-Deoxy-d-arabino-heptulosonate-7-phosphate synthetase 100 Inorganic pyrophosphatase 101 Oxalate decarboxylase 101 Oxalate oxidase 101 Isopentenyl diphosphate isomerase 102 2-C-methyl-d-erythritol 2,4-cyclodiphosphate synthase 103 Enzymes with Binuclear Active Sites 103 Aminopeptidases 104 Arginase 104 Proclavaminate amidino hydrolase 104 Catalase 105 Protein phosphatases 106 Purple acid phosphatase 106 Protein phosphatases 106 Phosphoglycerate mutase 107 Glutamine synthetase 107 Isomerases 109 Transferases 110 Ribosyltransferases 111 Galactosyltransferases 111 Glucosyltransferases 112 Enzymes with Trinuclear Active Sites 113 Bifunctional inositol monophosphatase/fructose 1,6-bisphosphatase 113 Enzymes with Tetranuclear Active Sites 114 The oxygen-evolving complex of photosystem II 114 Acknowledgement 115 References 115 5.2 Technetium 131 Introduction 132 Systematic Chemistry 137 Oxidation state (VII) 137 Complexes with oxo-ligands 138 Nitrido- and imido-ligands 141 Oxidation State (VI) 145 Binary halogen and halogen/oxo-containing complexes 145 Nitrido and imido ligands 145 Oxo-sulfur and nitrogen ligands 150 Oxidation State (V) 151 Compounds containing no multiply bonded ligands 152 Oxo-complexes, the "[Tc=O]3+" core 153 Oxygen ligands including macrocycles 154 Sulphur ligands 157 Nitrogen ligands including macrocycles 160 Mixed NO donor ligands 164 Mixed NS-donor ligands 170 Complexes of N,S ligands with mixed-ligand coordination 178 Mixed X,P ligands 178 Tertiary phosphine and arsine complexes 179 Imido and nitrido complexes 184 With monodentate ligands 184 With polydentate ligands 187 Imido complexes 196 Hydrazido, diazenido, and diazene complexes 198 Oxidation State (IV) 202 Halide and pseudohalide complexes 202 Complexes with oxygen ligands 204 Nitrogen ligands 207 Sulfur ligands 207 Tertiary phosphine and arsine complexes 208 Mixed-donor-set polydentate ligands 208 Oxidation State (III) 210 Tertiary phosphine and arsine ligands 211 Nitrogen and oxygen ligands 213 Oxygen ligands 217 Sulfur and mixed P,S and P,N and P,O ligands 219 Dinuclear TcIII complexes containing multiple bonds 224 Oxidation State (II) 229 Nitrosyl and thionitrosyl complexes 229 Heterocyclic amine ligands 231 Tertiary phosphine and arsine ligands in combination with other donors 232 Complexes of TcII with Tc=Tc multiple bonds 236 Oxidation State (I) 236 Complexes containing C and P ligands 237 Tertiary phosphines and dihydrogen complexes 240 Dinitrogen complexes and nitrogen ligands 241 Nitrosyl and thionitrosyl ligands 242 CO complexes 244 Selected Topics in Technetium Chemistry 244 99Tc NMR spectroscopy 244 Radiopharmaceutical Technetium-Chemistry 249 Co-ordination Complexes for Radiopharmaceutical Applications 250 Heart imaging agents 250 Brain-imaging agents 252 Kidney- and bone-imaging agents 254 Multidrug resistance 256 Hypoxia-imaging agents 256 Second-generation Technetium-based Radiopharmaceuticals 257 Intrinsic receptor binding 259 Conclusion 261 Acknowledgement 261 References 261 5.3 Rhenium 275 Introduction 276 Systematic Chemistry 276 Oxidation State VII 276 Complexes with oxo ligands 277 Perrhenate complexes 277 Compounds derived from Re2O7 278 Trioxo complexes 280 Dioxo and monoxo complexes 282 Sulfido complexes 282 Nitrido and imido and related complexes 283 Supramolecular compounds 285 Oxidation State VI 286 Oxo complexes 287 Nitrido and imido complexes 287 Miscellaneous 289 Oxidation State V 290 Oxo complexes 290 Complexes containing exclusively monodentate ligands 291 Complexes with chelating ligands 297 Sulfido complexes 321 Nitrido complexes 322 Complexes containing exclusively monodentate ligands 322 Complexes containing chelating ligands 323 Complexes with Bridging Nitrido Ligands 326 Imido complexes 329 Complexes containing exclusively monodentate ligands 330 Complexes containing chelating ligands 331 Miscellaneous 335 Oxidation State IV 336 Complexes containing exclusively monodentate ligands 336 Halide and pseudohalide ligands 336 Ligands with P, O, N, S, or As donor atoms 337 Complexes with chelating ligands 338 Phosphorus, nitrogen donor and mixed N/S and N/O donor ligands 338 Sulfur and oxygen donor and mixed S/O donor ligands 340 Oxidation state III 341 Complexes containing exclusively monodentate ligands 342 Ligands with phosphorus or nitrogen donor ligands 342 Ligands with sulfur donors and mixed-ligand complexes 344 Complexes with chelating ligands 345 Phosphorus and arsenic donor ligands 345 Nitrogen donor ligands 347 Sulfur and oxygen donor atoms 349 Mixed-donor N/O- and N/S-ligands 350 Mixed-donor P/O-, P/N-, P/S-, and S/O-ligands 352 Oxidation state II 354 Phosphorus donor ligands 354 Nitrogen and sulfur donor ligands 355 Oxidation state I 357 Complexes containing exclusively monodentate ligands 357 Phosphorus donor ligands 357 Selected isocyanide complexes 359 Complexes with chelating ligands 359 Phosphorus donor ligands 359 Nitrogen donor ligands 362 Miscellaneous 363 Rhenium(I) tricarbonyl complexes 364 Oxidation state 0 365 Nitrosyl, Thionitrosyl, and Related Complexes 367 Halide and pseudohalide ligands 367 Phosphorus donor ligands 367 Sulfur, nitrogen, and oxygen donor ligands 369 Thionitrosyl complexes 370 Hydrazido and Related Complexes 371 General considerations 371 Complexes with a single hydrazide ligand 372 Complexes with two and more hydrazide ligands 374 Hydrido complexes 376 Phosphorus and arsenic donor ligands 377 Nitrogen donor ligands 380 Sulfur donor ligands and miscellaneous 381 Bi- and multinuclear hydrides 382 Rhenium Compounds And Nuclear Medicine 384 Small Molecules 384 Direct Peptide and Protein Labeling and Bioconjugates 385 References 386 5.4 Iron 407 General Survey 409 Introduction 409 The Element 409 Oxidation States 410 Spin States; Spin Cross-over 412 Spectroscopy 414 Kinetics and Mechanisms 415 Size and Solvation 415 Stability Constants and Speciation 417 Tripodal and Encapsulating Ligands 418 Template and Supramolecular Chemistry 418 Applications and Relevance 419 Analysis 419 Pigments and colorants 420 Nutrition, metabolism, and pharmacology 420 Geochemical and environmental aspects 425 Group 14 Donors 426 Cyanide-Hexacyanoferrates 426 Mononuclear hexacyanoferrates 426 Hexacyanoferrate(II) 426 Hexacyanoferrates(III) 426 Hexacyanoferrate(II)/(III) electron exchange 426 Kinetics of hexacyanoferrate reductions and oxidations 426 Polynuclear and mixed valence complexes 427 Polynuclear complexes 427 Mixed valence complexes 428 Cyanide-Pentacyanoferrates 429 Introduction 429 Solvatochromism and piezochromism 429 Formation and dissociation kinetics 429 Aqueous media 429 Medium effects 432 Pentacyanoferrates(III) 432 Redox chemistry 432 Formation of, and electron transfer within, binuclear species 432 Pentacyanonitrosylferrate(II) 433 Other Cyano-complexes 434 Tetracyanoferrates and dicyanoferrates 434 Carbonyl cyanides 434 Other Ligands 436 Group 15 Donors 436 Dinitrogen, Ammonia, and Amines 436 Thiocyanate 437 Azide 437 Iron(II) 437 Iron(III) 437 Pyridines, Pyrazines, and Triazines 438 Pyrazines and triazines 441 Diimine and Related Ligands 441 General 441 Preparations, properties, and structures 442 1,10-Phenanthroline, 2,2`-bipyridyl, and related ligands 442 Schiff base and diazabutadiene complexes 446 Spectroscopy and magnetism 447 Spectroscopy 447 Magnetism-spin states and spin cross-over 447 Solution properties 449 Kinetics and mechanisms 449 Aquation and ligand replacement 449 Base hydrolysis 451 Cyanide attack 453 Racemization and isomerization 453 Redox reactions 454 Lower oxidation states 454 Binuclear complexes 455 Bridging diimines 455 Tetradentate bis-diimine ligands 456 Quaterpyridyl and hexapyridyl 457 Diimine-cyanide complexes 459 Solutions, solvation, solvatochromism, and piezochromism 459 Kinetics and mechanisms 460 Structures; other properties 461 Diimine-thiocyanate complexes 461 Spin cross-over 461 Other ternary diimine complexes 461 Dioximes and monoximes 462 Azoles 462 Pyrroles 462 Imidazoles and pyrazoles 463 Imidazoles 463 Pyrazoles 463 Triazoles 464 Tetrazoles 465 Thiazoles 465 Macrocyclic Ligands 466 Triaza-, tetraaza-, and hexaaza-macrocycles 466 Porphyrin complexes 468 General 468 Synthesis and properties 469 Structures 469 Spin states 470 Solubilization 471 Kinetics and mechanisms of substitution and addition 471 Redox properties and electrochemistry 471 Porphycene, porphyrazine, and corrole complexes 472 Phthalocyanine complexes 473 Nitric Oxide Complexes 473 Other N-donor Ligands 476 Phosphorus Donor Ligands 476 Group 15/16 Donors 478 Nitrogen and Oxygen Donors 478 Oxines 478 Schiff bases 478 Spin cross-over 478 Acyclic polyaminocarboxylates 480 Polyazamacrocycles with pendant carboxylates 482 Other N,O donors 482 Nitrogen and Sulfur Donors 485 Nitrogen, Oxygen, and Sulfur Donors 486 Group 16 Donors 487 Simple O-donor Ligands 487 Introduction 487 The aqua-ions-general 488 Aqua- and hydroxo-iron(II) 489 Oxidation of Fe2+aq 489 Solution properties 489 Complex formation 489 Aqua- and hydroxoaqua-iron(III) 489 General 489 Complex formation 490 Oxidation by Fe3+aq 491 mu-Oxo- and mu-hydroxo-aquairon(III) species 491 Alkoxides; phenoxide 492 Dioxygen, peroxide, and superoxide 492 Inorganic Oxoanions 493 Oxoanion complexes of Fe2+ and Fe3+ 493 Polyoxometallates 494 Organic Oxoanions 495 Iron(II) 495 Iron(III) 495 Binuclear and Polynuclear Complexes 496 Di-iron complexes 496 mu-Oxide 496 Supported mu-oxide-general 497 mu-Alkoxide; mu-oxide plus mu-alkoxide 497 mu-Carboxylate 497 mu-Oxide with mu-carboxylate 498 mu-Hydroxide with mu-carboxylate 498 mu-Carboxylate with mu-alkoxide or mu-phenoxide 499 mu-Carboxylate with other mu-ligands 500 Oxotri-iron complexes 500 Other polynuclear complexes 501 Diketones and Hydroxyketones 504 beta-Diketones and hydroxyketones-general 504 beta-Diketones 504 Hydroxyketones 504 Hydroxypyranones and hydroxypyridinones 505 Introduction 505 Preparation of ligands for complexes 505 Preparations, properties, and structures 507 Iron transfer and removal 508 Analytical applications 509 Siderophores and Models 509 Catechols 509 Monocatecholates 509 Biscatecholates 510 Triscatecholates 510 Polycatecholates 515 Hydroxamates 515 Comparisons 520 Other O-donor Ligands 522 O,S-donor Ligands 522 Sulfur Donors 523 Mononuclear species 523 Bi- and polynuclear complexes and clusters 524 Selenium and Tellurium Donors 526 Group 17 Donors 526 Fluoride Complexes 526 Chloride Complexes 526 Iron(II) 527 Iron(III) 527 Bromide Complexes 530 Iodide Complexes 530 Hydride and Dihydrogen Complexes 531 Abbreviations 531 References 533 5.5 Ruthenium and Osmium: Low Oxidation States 558 Introduction 559 Ruthenium(III) And Osmium(III) 559 Nitrogen-donor Ligands 559 Monodentate ligands 559 Didentate ligands 561 Macrocyclic ligands 561 Di- and trinuclear complexes 561 Phosphorus-, Arsenic-, and Antimony-donor Ligands 562 Oxygen-donor Ligands 563 Monodentate ligands 563 Didentate ligands 563 Tripodal ligands and polyoxometallates 564 Sulfur- and Selenium-donor Ligands 565 Monodentate ligands 565 Didentate ligands 565 Dinuclear complexes with bridging S22- ligands 566 Mixed-donor Atom Ligands 566 N,O-donors 566 N,S- and S,O-donors 570 Halide and Cyanide Ligands 570 Ruthenium(II) And Osmium(II) 570 Nitrogen-donor Ligands 570 Mononuclear complexes with simple ligands 570 [M(bpy)3]2+(M=Ru or Os; bpy=2,2'-bipyridine) and relatedheteroleptic complexes containing 2,2'-bipyridine, 2,2'-bipyrimidine, and 2,2'-bipyrazine 577 Mononuclear complexes of general formula [Ru(bpy)2L2]n= and complexes containing functionalized bpy ligands 586 Dinuclear complexes of the general formula [(bpy)2M(mu-L)M(bpy)2]n+(M=Ru or Os) 605 Polynuclear complexes (M=Ru or Os, n greater than or equal to 3) containing M(bpy)2 units 618 Stereochemical aspects of [M(bpy)3]2+ and related complexes 621 Complexes containing 1,10-phenanthroline or related ligands 624 Mononuclear complexes containing didentate N,N-donor ligands other than bpy or phen 627 Mononuclear complexes of type [M(bpy)L4]n+ (L=monodentate ligand) 631 Dinuclear complexes (M=Ru or Os) containing M(NH3)5 or related units 632 Heterometallic (M=Ru or Os, M`not equal to Ru or Os) dinuclear and polynuclear complexes 632 Mixed-valence dinuclear complexes 634 Complexes containing M(bpy) units coupled to macrocyclic or calix[4]arene recognition domains 637 Complexes containing 2,2':6',2''-terpyridine ligands and cyclometallated analogs 639 Complexes containing ligands with N,N',N''- or N,C,N'-donor sets excluding tpy and tripodal ligands 649 Complexes containing [HBpz3]-, HCpz3 (pz=pyrazolyl), and related ligands 651 Complexes containing noncyclic ligands with N,N',N'',N'''-donor sets 652 Complexes containing porphyrin ligands 653 Complexes containing phthalocyanine ligands 657 Complexes containing aza-macrocyclic ligands 658 Complexes with miscellaneous N-donor heterocyclic ligands 658 Interactions of ruthenium(II) complexes with DNA and related work 659 Complexes as models for Photosystem II 666 Phosphorus-, Arsenic-, and Antimony-donor Ligands 667 Mononuclear complexes containing monodentate ligands 667 Mononuclear complexes containing didentate ligands 668 Mononuclear complexes containing tridentate and tetradentate ligands 673 Dinuclear complexes 675 Development of water-soluble catalysts 675 Oxygen-donor Ligands 677 Sulfur-donor Ligands 679 Mononuclear complexes 679 Di- and trinuclear complexes 683 Selenium- and Tellurium-donor Ligands 685 Mixed-donor Atom Ligands 685 N,O-donors 685 N,P-donors 688 N,S-donors 689 P,O- and P,S-donors 692 S,O- and N,O,S-donors 694 Mononuclear Complexes with Cyanide or Fluoride Ligands 694 Dinuclear Complexes Of MIII And MII Containing Halo-Bridges 695 Dinuclear Complexes Containing Carboxylate And Related Bridging Ligands 696 Ruthenium And Osmium Complexes ContainingHydride And Dihydrogen Ligands 699 Ruthenium(0) And Osmium(0) 703 Acknowledgement 703 References 703 5.6 Ruthenium and Osmium: High Oxidation States 735 Introduction 736 Ruthenium(VIII) and Osmium(VIII) 738 Imido Complexes 738 Nitrido Complexes 739 Oxo Complexes 741 Metal tetroxides 741 RuO4 741 OsO4 741 Oxo hydroxo complexes 743 Oxo halo complexes 743 Ruthenium(VII) and Osmium(VII) 745 Imido Complexes 745 Nitrido Complexes 745 Oxo Complexes 745 [RuO4]- 745 [OsO4]- 746 Oxo fluoro species 746 Ruthenium(VI) and Osmium(VI) 746 Imido Complexes 746 Mono imido complexes 746 Oxo imido complexes 747 Bis imido complexes 748 Tris imido complexes 751 Imido-bridged complexes 752 Nitrido Complexes 752 Carbon ligands 752 Cyano complexes 752 Alkyl complexes 752 Nitrogen ligands 752 Syntheses 752 Reactivities 756 Electronic absorption and emission spectroscopy 761 Phosphorus, arsenic, and antimony donor ligands 763 Oxygen and sulfur ligands 763 Oxygen ligands 763 Sulfur ligands 763 Halogen ligands 765 Mixed donor atom ligands 765 Porphyrins and related complexes 767 Hydrazido Complexes 768 Oxo Complexes 768 Carbon ligands 771 Carbonyl complexes 771 Cyano complexes 771 Alkyl and aryl complexes 771 Nitrogen ligands 772 Syntheses 772 Electrochemistry 779 Reactivities 786 Phosphorus and arsenic ligands 792 Oxygen ligands 792 Sulfur and selenium ligands 795 Halogen ligands 795 Mixed donor atom ligands 796 Macrocyclic tertiary amine ligands 798 Porphyrins and related complexes 799 Syntheses 799 Reactivities 800 Sulfur Complexes 801 Halide Complexes 801 Fluoro complexes 801 Chloro, bromo, and iodo complexes 802 Hydride Complexes 802 Miscellaneous 802 Ruthenium(V) and Osmium(V) 802 Imido Complexes 802 Nitrido Complexes 803 Miscellaneous Nitrogen Ligands 803 Hydrazido complexes 803 Phosphoraniminato complexes 804 Sulfilimido complexes 805 Oxo Complexes 805 Terminal oxo complexes 805 Carbon ligands 805 Nitrogen ligands 806 Oxygen ligands 809 Oxo-bridged species 809 Alkoxo Complexes 811 Sulfur Ligands 811 Halide Ligands 811 Ruthenium(IV) And Osmium(IV) 811 Amido Complexes 811 Nitrogen donor ligands 811 Oxygen donor ligands 813 Mixed donor atom ligands 813 Porphyrin and related ligands 813 Imido Complexes 814 Nitrido Complexes 815 Mononuclear complexes 815 Binuclear and trinuclear nitrido-bridged complexes 815 Miscellaneous Nitrogen Ligands 817 Cyanoimido complexes (NCN) 817 Methyleneamido complexes (N=CR2) 818 Azidoimido complexes (NN3) 818 Hydrazido complexes (NNR2) 818 Sulfilimido and sulfoximido complexes 819 Phosphoraniminato (NPR3) and phosphineaminato (NHPR3) complexes 820 Other nitrogen ligands 822 Phosphine, Arsine, and Stibine Ligands 823 Oxo Complexes 823 Mononuclear complexes 823 Synthesis 823 Electrochemistry 826 Reactivities 828 Oxo-bridged dimers 830 Nitrogen ligands 830 Oxygen ligands 832 Halide ligands 833 Miscellaneous Oxygen Ligands 833 Complexes containing alkoxo ligands 833 Complexes containing peroxo ligands 834 Complexes containing dioxolene ligands 834 Sulfur Ligands 834 Thioether complexes 834 Thiolato complexes 835 Metallothioanions as ligands 837 Sulfido complexes 837 Miscellaneous sulfur ligands 837 Dithiocarbamato (S2CNR2-) complexes 837 Dithiolene complexes 837 Halide Ligands 838 Hydride Ligands 839 References 839 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.