Comprehensive coordination chemistry: the synthesis, reactions, properties & applications of coordination compounds

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