Comprehensive Coordination Chemistry Synthesis Reactions: Properties & Applications Coordination Compounds Ligands (Comprehensive Coordination Chemistry Synthesis Reactions)

Volume 2: Ligands......Page 4 Contents......Page 6 Preface......Page 10 Contributors to Volume......Page 12 Contents of All Volumes......Page 16 11.2 COMPOUNDS WITH MERCURY TO TRANSITION METAL BONDS......Page 20 11.3 POLYATOMIC CATIONS OF MERCURY......Page 22 11.4 REFERENCES......Page 23 12.1.2 GENERAL PROPERTIES OF CYANlDE AS A LIGAND......Page 26 12.1.3 CYANO COMPLEXES: PREPARATIVE METHODS AND REACTIONS......Page 28 12.1.4 CYANO COMPLEXES STRUCTURES AND THERMODYNAMICS......Page 29 12.1.5 FULMINATO COMPLEXES......Page 31 12.1.6 REFERENCES......Page 33 12.2.2 REFERENCES......Page 34 13.1.1 INTRODUCTION......Page 42 13.1.2 AMMONIA AND AMMINES......Page 45 13.1.3 MONOAMINE LIGANDS......Page 47 13.1.4 DIAMINE LIGANDS......Page 49 13.1.5 TRIAMINE LIGANDS......Page 63 13.1.6 TETRAMINE LIGANDS......Page 69 13.1.7 PENTAMINE LIGANDS......Page 75 13.1.8 HEXAMINE LIGANDS......Page 77 13.1.9 AMINOBENZENE LIGANDS......Page 78 13.1.10 REFERENCES......Page 79 13.2.1 INTRODUCTION, SCOPE AND LIMITATIONS......Page 92 13.2.2 WHY ARE HETEROCYCLIC NITROGEN ATOMS GOOD LIGAND DONOR ATOMS?......Page 93 13.2.3 LIGANDS CONSISTING OF MONOCYCLIC RINGS......Page 95 13.2.4 LIGANDS CONSISTING OF A MONOCYCLIC RING WITH AN ADDITIONAL LIGAND GROUP AS A SUBSTITUENT......Page 101 13.2.5 FLEXIBLE CHELATING LIGANDS CONTAINING TWO OR MORE HETEROCYCLIC LIGANDS......Page 103 13.2.6 CONDENSED OR CONJUGATED HETEROCYCLIC CHELATING LIGANDS......Page 108 13.2.7 CONCLUDING REMARKS......Page 113 13.2.8 REFERENCES......Page 114 13.3 Miscellaneous Nitrogen-containing Ligands......Page 118 13.3.1 INTRODUCTION......Page 119 13.3.2 NITROSYL COMPLEXES......Page 120 13.3.3 THIONITROSYL COMPLEXES......Page 137 13.3.4 PHOSPHINIMINATO COMPLEXES......Page 141 13.3.5 METHYLENEAMIDO COMPLEXES......Page 144 13.3.6 DIAZENIDO COMPLEXES......Page 149 13.3.7 HYDRAZIDO(2 -) AND HYDRAZIDO(1 -) COMPLEXES......Page 160 13.3.8 REFERENCES......Page 170 13.4 Amido and Imido Metal Complexes......Page 180 13.4.2 SYNTHESIS OF METAL AMIDES AND IMIDES......Page 181 13.4.3 PHYSICAL AND SPECTROSCOPIC PROPERTIES......Page 187 13.4.4 SOLID STATE AND MOLECULAR STRUCTURES......Page 189 13.4.5 EVIDENCE FOR AND CONSEQUENCES OF AMIDO AND IMIDO LIGAND-TO-METAL pi-BONDING......Page 195 13.4.6 REACTIONS OF AMIDE AND IMIDE LIGANDS......Page 198 13.4.7 REFERENCES......Page 203 13.5 Sulfurdiimine Triazenido Azabutadiene and Triatomic Hetero Anion Ligands......Page 208 13.5.1 SULFURDIIMINE AND THIONITRITE METAL COMPLEXES......Page 209 13.5.2 TRIAZENIDO AND AMIDINO METAL COMPLEXES......Page 214 13.5.3 1,4-DIAZA-1,3-BUTADIENE (a-DIIMINE) METAL COMPLEXES......Page 225 13.5.4 TETRAAZA-1,3-BUTADIENE METAL COMPLEXES......Page 236 13.5.5 METAL COMPLEXES OF TRIATOMIC HETERO ANIONS .........Page 244 13.5.6 REFERENCES......Page 257 13.6.1 INTRODUCTION......Page 264 13.6.2 GENERAL FEATURES......Page 265 13.6.3 COMPLEXES OF THE TRANSITION METALS......Page 267 13.6.4 BIOLOGICAL APPLICATIONS......Page 274 13.6.5 RELATED POLYWRAZOLYL LIGANDS......Page 275 13.6.8 REFERENCES......Page 276 13.7.1 INTRODUCTION......Page 280 13.7.2 STRUCTURES......Page 281 13.7.4 REACTIONS......Page 283 13.7.5 REFERENCES......Page 285 13.8.1 OXIMES......Page 288 13.8.2 AMIDINE COMPLEXES......Page 294 13.8.3 IMIDATE ESTERS......Page 295 13.8.4 IMINE (RN=CR) COMPLEXES......Page 298 13.8.5 GUANIDINES, BIGUANIDES AND RELATED LIGANDS......Page 300 13.8.6 UREA AND URYLENE COMPLEXES......Page 304 13.8.7 REFERENCES......Page 306 14 Phosphorus, Arsenic, Antimony and Bismuth Ligands......Page 1008 14.2 SYNTHESIS......Page 1009 14.3 THE CONE ANGLE CONCEPT......Page 1031 14.4 BONDING IN COMPLEXES OF PNICTIDE LIGANDS......Page 1049 14.5 SOME RECENT DEVELOPMENTS......Page 1060 14.6 P4 AND FRAGMENTS......Page 1075 14.7 REFERENCES......Page 1080 15.1.1 INTRODUCTION......Page 314 15.1.2 WATER HYDRONDE AND OXIDE AS BRIDGING LIGANDS......Page 317 15.1.4 PROPERTIES......Page 324 15.1.5 REFERENCES......Page 330 15.2.2 DIOXYGEN......Page 334 15.2.3 THEORETICAL CONSIDERATIONS......Page 335 15.2.4 MONONUCLEAR PEROXO COMPLEXES......Page 337 15.2.5 MONONUCLEAR SUPEROXO COMPLEXES......Page 340 15.2.7 BINUCLEAR SUPEROXO COMPLEXES......Page 342 15.2.8 METAL-PORPHYRIN COMPLEXES......Page 344 15.2.9 REACTIONS OF METAL-DIOXYGEN COMPLEXES......Page 347 15.2.10 REFERENCES......Page 349 15.3 AIkoxides and Aryloxides......Page 354 15.3.2 SYNTHESIS OF METAL ALKOXIDES AND PHENOXIDES......Page 355 15.3.3 PHYSICAL AND SPECTROSCOPIC PROPERTlES OF METAL ALKOXIDES AND ARYLOXIDES, M(OR)x......Page 363 15.3.4 SOLID STATE AND MOLECULAR STRUCTURES......Page 367 15.3.5 REACTIONS OF METAL ALKOXIDES AND ARYLOXIDES......Page 370 15.3.6 ORGANOMETALLIC CHEMISTRY SUPPORTED BY ALKOXIDE LIGANDS......Page 374 15.3.7 REFERENCES......Page 379 15.4.1 INTRODUCTION......Page 384 15.4.2 STRUCTURE OF METAL beta-DIKETONATE COMPLEXES......Page 389 15.4.3 SYNTHESIS OF METAL beta-DIKETONATE COMPLEXES......Page 393 15.4.4 REACTIONS OF METAL beta-DIKETONATES......Page 397 15.4.5 COMPLEX FORMATION AND beta-DIKETONATE DISPLACEMENT......Page 405 15.4.6 ORGANOMETALLIC CHEMISTRY AND CARBON-BONDED beta-DIKETONATES......Page 411 15.4.7 TROPOLONATES AND QUINONES......Page 416 15.4.8 POLYKETONE COMPLEXES......Page 418 15.4.9 COMPLEXES OF NEUTRAL beta-DIKETONES......Page 420 15.4.10 REFERENCES......Page 422 15.5.1 INTRODUCTION......Page 432 15.5.2 CLASSIFICATION OF OXYANIONS AS LIGANDS......Page 434 15.5.3 STRUCTURAL DATA ON COORDINATED OXYANIONS......Page 438 15.5.4 ONE-COORDINATE OXYANIONS......Page 441 15.5.5 TWO-COORDINATE OXYANIONS......Page 444 15.5.6 THREE-COORDINATE OXYANIONS......Page 446 15.5.7 FOUR- TO TWELVE-COORDINATE OXYANIONS......Page 448 15.5.10 SUMMARY OF THE OXYANIONS AS LIGANDS......Page 450 15.5.11 REFERENCES......Page 452 15.6.1 INTRODUCTION......Page 454 15.6.2 MONOCARBOXYLATES......Page 455 15.6.3 DICARBOXYLATES AND RELATED SPECIES......Page 462 15.6.4 CARBONATES......Page 465 15.6.5 CARBAMATES......Page 469 15.6.6 CARBON DIOXIDE COMPLEXES......Page 470 15.6.7 SQUARATES AND RELATED SPECIES......Page 472 15.6.8 REFERENCES......Page 475 15.7.1 INTRODUCTION......Page 480 15.7.2 NOMENCLATURE......Page 481 15.7.3 ACID-BASE PROPERTIES......Page 484 15.7.4 SPECTROSCOPIC AND CHIROPTICAL PROPERTIES......Page 486 15.7.5 STRUCTURAL PROPERTIES OF COORDINATED HYDROXY ACIDS......Page 490 15.7.6 REFERENCES......Page 502 15.8.1 SULFOXIDES AND SELENOXIDES......Page 506 15.8.2 FORMAMIDE, ACETAMIDE AND RELATED LIGANDS......Page 509 15.8.3 AMINE N-OXIDES......Page 513 15.8.4 PHOSPHINE OXIDES, ARSINE OXIDES AND RELATED LIGANDS......Page 516 15.8.5 REFERENCES......Page 520 15.9.1 HYDROXAMATES......Page 524 15.9.2 CUPFERRON, NEOCUPFERRON AND RELATED LIGANDS......Page 528 15.9.3 REFERENCES......Page 532 16.1 Sulfides......Page 534 16.1.2 H2S AND RSH AS LIGANDS......Page 535 16.1.3 HYDROSULFIDO (SH-) COMPLEXES......Page 536 16.1.4 SULFIDE (S2-) AS A LIGAND......Page 538 16.1.5 THIOLATES (SR-)......Page 545 16.1.6 THE DISULFIDO LIGANDS6......Page 550 16.1.7 POLYSULFIDO LIGANDS......Page 559 16.1.9 REFERENCES......Page 566 16.2.1 SURVEY OF COMPOUND TYPES WITH THIOETHER LIGANDS......Page 570 16.2.2 FORMATION AND DISPLACEMENT REACTIONS......Page 572 16.2.3 STRUCTURE AND BONDING......Page 574 16.2.5 REFERENCES......Page 576 16.3.1 DISCRETE THIlOMETALATE IONS - PROPERTIES, ELECTRONIC STRUCTURE AND REACTIVITY......Page 578 16.3.2 GENERAL SURVEY OF COMPOUND TYPES......Page 581 16.3.3 SPECTROSCOPIC PROPERTIES AND CHEMICAL BONDING......Page 589 16.3.5 REFERENCES......Page 595 16.4.1 INTRODUCTION......Page 598 16.4.2 CARBON DISULFIDE AND CARBON MONOSULFIDE AS LIGANDS......Page 599 16.4.3 CS2- AND COS-BASED LIGANDS......Page 603 16.4.5 REFERENCES......Page 610 16.5.1 INTRODUCTION......Page 614 16.5.2 SYNTHESES AND TYPES OF DITHIOLENES......Page 616 16.5.3 CHARACTERIZATION AND PROPERTIES OF DITHIOLENES......Page 627 16.5.4 USEFUL PROPERTIES OF DITHIOLENES......Page 641 16.5.5 REFERENCES......Page 646 16.6 Other Sulfur-containing Ligands......Page 652 16.6.1 OXIDES OF SULFUR......Page 653 16.6.2 THIOSULFATE ION......Page 655 16.6.3 SULFITE ION......Page 656 16.6.4 THIOUREA AND ITS DERIVATIVES......Page 658 16.6.5 SULFOXIDES......Page 659 16.6.6 ORGANOPHOSPHORUS SULFIDES AND RELATED LIGANDS......Page 660 16.6.8 1,5-DITHIACYCLOOCTANE......Page 663 16.6.9 THIOCARBOXYLIC ACIDS......Page 664 16.6.10 THIOCARBOXAMIDES......Page 666 16.6.11 MONOTHIO-beta-DIKETONES......Page 667 16.6.12 DITHIO-beta-DIKETONES......Page 672 16.6.13 beta-MERCAPTO KETONES, ESTERS, THIOESTERS AND AMIDES......Page 673 16.6.14 REFERENCES......Page 675 17.1 INTRODUCTION......Page 680 17.2 SELENIUM LIGANDS......Page 681 17.3 TELLURIUM LIGANDS......Page 687 17.5 REFERENCES......Page 691 18.2 PHYSICAL PROPERTIES OF THE HALOGENS......Page 694 18.4 BRIDGE BOND FORMATION......Page 696 18.5 HIGHER COORDINATION NUMBERS......Page 703 18.6 REFERENCES......Page 706 19.1 INTRODUCTION......Page 708 19.2 TYPES OF HYDRIDE COMPLEX......Page 709 19.3 PREPARATION OF HYDRIDE COMPLEXES......Page 713 19.4 PHYSICAL PROPERTIES......Page 718 19.5 CHEMICAL PROPERTIES......Page 725 19.6 REFERENCES......Page 730 20.1.1 INTRODUCTlON......Page 734 20.1.2 MONODENTATE SCHIFF BASES......Page 737 20.1.3 BIDENTATE SCHIFF BASES......Page 739 20.1.4 TRIDENTATE SCHIFF BASES......Page 745 20.1.6 MULTIDENTATE SCHIFF BASES......Page 752 20.1.8 REFERENCES......Page 754 20.2 Amino Acids Peptides and Proteins......Page 758 20.2.2 AMINO ACIDS......Page 759 20.2.3 PEPTIDES......Page 777 20.2.4 PROTEINS......Page 788 20.2.6 REFERENCES......Page 793 20.3.1 INTRODUCTION......Page 796 20.3.2 SYNTHESES......Page 797 20.3.3 EDTA AND ITS HOMOLOGUES......Page 798 20.3.4 TETRACARBOXYLIC ACIDS WITH SUBSTITUENTS......Page 804 20.3.5 OTHER COMPLEXONES......Page 806 20.3.6 APPLICATIONS......Page 809 20.3.7 REFERENCES......Page 810 20.4.1 INTRODUCTION AND SCOPE......Page 812 20.4.2 BIDENTATE NITROGEN-OXYGEN LIGANDS......Page 813 20.4.3 BIDENTATE NITROGEN-SULFUR LIGANDS......Page 818 20.4.4. BIDENTATE SULFUR-OXYGEN LIGANDS......Page 823 20.4.5 MIXED DONOR BIDENTATES CONTAINING SELENIUM......Page 825 20.4.6 REFERENCES......Page 828 21.1 Porphyrins, Hydroporphyrins, Azaporphyrins, Phthalocyanines, Corroles, Corrins and Related MacrocycIes......Page 832 21.1.1 PORPHYRINS AND HYDROPORPHYRINS......Page 833 21.1.2 AZAPORPHYRINS......Page 875 21.1.3 CORROLES AND CORRINS......Page 890 21.1.4 PENTAPYRROLIC MACROCYCLES AND RELATED COMPOUNDS......Page 907 21.2.1 INTRODUCTION......Page 918 21.2.2 METHODS OF PREPARATION......Page 919 21.2.3 MODIFICATION OF PREFORMED AZA MACROCYCLE COMPLEXES......Page 924 21.2.5 PROPERTIES OF AZA MACROCYCLE COORDINATION COMPOUNDS......Page 926 21.2.6 REFERENCES......Page 932 21.3 Multidentate Macrocyclic and Macropolycyclic Ligands......Page 934 21.3.1 INTRODUCTION......Page 935 21.3.2 CLASSIFICATIONS OF LIGANDS, SUBSTRATES AND COMPLEXES......Page 936 21.3.3 STRATEGIES TO ARCHITECTURAL DESIGN......Page 941 21.3.4 SYNTHETIC PROCEDURES......Page 943 21.3.5 METAL CATION COMPLEXES......Page 946 21.3.6 MOLECULAR CATION COMPLEXES......Page 962 21.3.7 ANION COMPLEXES......Page 967 21.3.8 NEUTRAL MOLECULAR COMPLEXES......Page 971 21.3.9 REFERENCES......Page 972 22.1 GENERAL CONSIDERATIONS......Page 978 22.2 CARBOXYLIC AND PHENOLIC ACIDS......Page 980 22.3 AMINO ACIDS......Page 983 22.4 PEPTIDES......Page 985 22.5 NON-PEPTIDE-BASED IONOPHORES......Page 991 22.6 PROTEINS......Page 993 22.7 NUCLEIC ACIDS AND SUBUNITS......Page 995 22.8 PORPHYRINS AND RELATED COMPOUNDS......Page 999 22.9 CARBOHYDRATES......Page 1003 22.11 REFERENCES......Page 1004 Subject Index......Page 1086 Formula Index......Page 1124