Comprehensive Coordination Chemistry II. Bio-coordination Chemistry

Cover Page......Page 1
Introduction to Volume 9......Page 2
COMPREHENSIVE COORDINATION CHEMISTRY II......Page 4
Volumes......Page 5
Info on Volume 9......Page 6
9.1 Metal Complexes as Catalysts for Polymerization Reactions......Page 8
Introduction......Page 9
Isospecific propylene polymerization......Page 10
Elastomeric poly(propylene)......Page 12
Constrained geometry catalysts......Page 13
Nitrogen-based ligands......Page 14
Oxygen based ligands......Page 17
Group 3 and rare earth metal catalysts......Page 18
Group 5 metal catalysts......Page 19
Nitrogen- and oxygen-based ligands......Page 20
Group 8 metal catalysts......Page 21
Group 10 metal catalysts......Page 22
Main group metal catalysts......Page 24
Coordinative Polymerization of Styrenes......Page 25
Atom Transfer Radical Polymerization of Styrenes......Page 27
Anionic Initiators of the group 1, 2, and 3 Metals......Page 30
Well-defined Magnesium and Aluminum Initiators......Page 31
Lanthanide Initiators......Page 33
Early Transition Metal Initiators......Page 34
Titanacyclobutanes......Page 36
Group 6 Metal Initiators......Page 37
Ruthenium Initiators......Page 40
Introduction......Page 43
Aluminum-based Initiators......Page 44
Magnesium and Zinc Initiators......Page 49
Calcium Initiators......Page 50
Tin Initiators......Page 51
iron Initiators......Page 52
Yttrium and Rare-earth Initiators......Page 53
Titanium and Zirconium Initiators......Page 58
Tetraphenylporphyrin Aluminum and Zinc Initiators......Page 59
Copolymerization of Epoxides and Aziridines with Carbon Monoxide......Page 61
Copolymerization of Epoxides and Aziridines with Carbon Monoxide......Page 64
Polymerization of Isocyanates and Guanidines......Page 65
References......Page 66
Introduction......Page 82
Homogeneous Hydrogenation......Page 83
Metal Monohydride Mechanism......Page 84
Metal Dihydride Mechanism......Page 87
Asymmetric Hydrogenation Mechanisms......Page 89
Homogeneous Transfer Hydrogenation......Page 99
Metal Monohydride Mechanism......Page 100
Metal-Ligand Bifunctional Concerted Mechanism......Page 102
Mechanism of Aerobic Alcohol Oxidation......Page 103
Homogeneous Hydrogenolysis......Page 105
Hydrodesulfurization......Page 106
Hydrodenitrogenation......Page 112
Hydrogenation in Aqueous Systems......Page 117
Water-soluble hydrogenation catalysts......Page 118
Immobilization on solids......Page 121
Immobilization via biphasic catalysis......Page 124
Microheterogenization on organized amphiphiles in the colloidal or nanoscale dimension......Page 125
Enantioselective hydrogenation in aqueous systems......Page 127
Hydrogenations with CO/H2O mixtures......Page 128
Hydrogenation in Supercritical Carbon Dioxide......Page 129
Hydrogenation by Cluster Catalysis......Page 132
Hydrogenation In Biological Systems......Page 136
References......Page 140
9.3 Metal Complexes as Catalysts for Addition of Carbon Monoxide......Page 147
Rhodium Catalysts......Page 148
Immobilization studies (see also Chapter 9.9)......Page 152
Palladium and Nickel Catalysts......Page 153
Reductive carbonylation......Page 154
Studies on the mechanism of catalytic hydroformylation......Page 155
Cis-PtCl2(diphosphine)/SnCl2 systems......Page 157
Miscellaneous......Page 158
Palladium......Page 159
Cobalt......Page 160
Introduction to phosphine catalysts......Page 161
Introduction to phosphite catalysts......Page 164
Chiral diphosphine ligands......Page 172
Diphosphite ligands......Page 175
Miscellaneous......Page 176
Diphosphines as chiral ligands......Page 177
Diphosphite ligands......Page 178
Phosphine-phosphite ligands......Page 180
Two-phase catalysis......Page 182
Palladium-Catalyzed Alternating Copolymerization of Alkenes And Carbon Monoxide......Page 185
Introduction......Page 190
Palladium catalysts......Page 191
Amidocarbonylation......Page 192
Cobalt catalysts......Page 193
Hydroxycarbonylation......Page 194
Palladium/Phosphorus Complexes in Hydroxycarbonylation......Page 195
Palladium Species Involved in the Hydroxycarbonylation Reaction......Page 196
Methoxycarbonylation......Page 197
Mechanistic studies......Page 198
Phosphorus ligands in Pd methoxycarbonylation......Page 199
References......Page 200
Introduction......Page 213
Epoxidation of Allylic Alcohols......Page 214
Epoxidation using metalloporphyrin as catalysts......Page 217
Epoxidation using metallosalen complexes as catalysts......Page 222
Epoxidation of Electron-deficient Olefins......Page 229
Oxidation of Enol Ethers and their Derivatives......Page 231
Asymmetric Aziridination......Page 233
General Features of Asymmetric Dihydroxylation......Page 237
Mechanistic Considerations......Page 241
Iron-mediated Dihydroxylation......Page 244
Asymmetric Aminohydroxylation......Page 245
Cu-catalyzed cyclopropanation......Page 249
Rh-catalyzed cyclopropanation......Page 251
Ru-catalyzed cyclopropanation......Page 254
Co-catalyzed cyclopropanation......Page 256
Cu-catalyzed cyclopropanation......Page 257
Rh-catalyzed cyclopropanation......Page 258
Ru-catalyzed cyclopropanation......Page 259
Co-catalyzed cyclopropanation......Page 260
Mechanism of Cyclopropanation......Page 261
Conclusion......Page 264
References......Page 265
Introduction......Page 271
Developments Since CCC (1987)......Page 272
Ligand Effects in Rhodium-catalyzed Hydroboration of  Vinylarenes......Page 275
Hydroboration of Substrates Containing C=C Bonds: Enynes and Alkynes......Page 276
Asymmetric Hydroboration......Page 277
Hydrocyanation......Page 281
Reactions of Nonactivated Alkenes......Page 282
Hydrocyanation of Activated Alkenes......Page 283
Developments in Achiral Catalytic Si-H Addition......Page 286
Asymmetric Hydrosilylation......Page 287
Enantioselective Hydrosilylation Employing Chiral Ferrocenyl Phosphine Ligands......Page 291
Intramolecular Asymmetric Hydrosilylation......Page 292
Mechanism and Early Transition Metal/Lanthanide Catalysts......Page 294
Rhodium and Iridium Catalysts......Page 297
Palladium and Platinum Catalysts......Page 300
Hydrophosphination (And Hydrophosphorylation)......Page 302
Hydrophosphination......Page 303
Hydrophosphorylation and Hydrophosphinylation......Page 304
References......Page 307
9.6 Metal Complexes as Catalysts for C-C Cross-coupling Reactions......Page 311
Introduction......Page 312
Major Methods of Cross-Coupling......Page 313
Cross-coupling with Organoboron Compounds......Page 314
Cross-coupling with Organotin Compounds......Page 316
Cross-coupling with Organozinc Reagents......Page 318
Cross-coupling with Organomagnesium and Organolithium Reagents......Page 321
Cross-coupling with Terminal Acetylenes......Page 322
The Development of the Cross-Coupling Methodology......Page 324
Mercury......Page 325
Indium......Page 326
Zirconium......Page 327
CH-nucleophiles......Page 328
Copper......Page 331
Activation of the nucleophilic reagent......Page 333
Compounds with Si-O bonds......Page 337
Tetraorganosilanes......Page 339
Leaving Groups......Page 340
Chlorides......Page 341
Esters as electrophiles in cross-coupling reactions......Page 342
Sulfur derivatives......Page 344
Se and Te derivatives......Page 346
Catalysts......Page 347
Chelating ligands with both phosphine and nonphosphine binding sites......Page 349
Bulky trialkyl- and dialkylphosphines......Page 351
Heterobimetallic complexes......Page 353
Phosphorus ligands other than phosphines......Page 354
Bidentate diphosphine ligands......Page 355
NC and OC-palladacycles......Page 357
Nonphosphorus ligands......Page 358
Heterocyclic carbene ligands......Page 359
Technological Aspects of Cross-coupling Chemistry......Page 362
Pd/C and Ni/C......Page 363
Polymer-immobilized catalysts......Page 364
Supercritical CO2......Page 365
References......Page 366
Introduction......Page 375
Early Examples......Page 377
Amination of aryl halides......Page 378
Amination of aryl triflates......Page 379
Third-generation Catalysts Bearing Alkylmonophosphines......Page 380
Sterically hindered bisphosphine ligands for aminations......Page 381
P,N, P,O, and dialkylphosphinobiaryl ligands......Page 382
Heterocyclic carbenes as ligands......Page 383
Aromatic C-N Bond Formation with Related Substrates......Page 384
Etherification......Page 387
Second-generation Catalysts Containing Sterically Hindered Alkylphosphines......Page 388
Carbon-Sulfur and Carbon-Selenium Bond-Forming Cross-Couplings......Page 390
Coupling of Aryl and Vinyl Halides with Phosphorus(V) Reagents......Page 392
Coupling of Aryl and Vinyl Halides with Phosphorus(V) Reagents......Page 393
Coupling with Silanes, Stannanes, and Germanes......Page 394
Coupling with Boranes......Page 395
Intermediates in the Coupling Chemistry......Page 396
References......Page 400
Alkali Metals......Page 405
Magnesium......Page 407
Scandium and Lanthanides......Page 408
Titanium......Page 411
Zirconium......Page 421
Hafnium......Page 422
Copper......Page 425
Silver and Gold......Page 427
Zinc......Page 428
Other Transition-Metal Lewis Acids......Page 430
Boron......Page 432
Aluminum......Page 435
Silicon......Page 436
Tin......Page 439
Others......Page 441
Conclusion/Classification of Lewis Acids......Page 443
References......Page 445
Introduction......Page 451
Incorporation by ion exchange reactions......Page 452
Incorporation by covalent anchoring......Page 455
Incorporation by ion exchange reactions......Page 456
Incorporating by covalent bonding......Page 457
Inorganic matrices......Page 458
Organic supports......Page 459
Supported Liquid Phase Catalysts (SLPC)......Page 460
Hydrogenation......Page 462
Supported titanium-based catalysts......Page 464
Supported salen-type complexes......Page 467
Heck reaction......Page 469
Trost-Tsuji allylic substitution......Page 471
Polymerization......Page 472
References......Page 473
9.10 Electrochemical Reactions Catalyzed by Transition Metal Complexes......Page 477
Basic Principles......Page 478
Metal Hydride Complexes: Electrogeneration and Electrocatalytic Dihydrogen Evolution......Page 479
Transition metal macrocycles......Page 480
Polypyridyl complexes......Page 481
Miscellaneous complexes......Page 482
Electrocatalytic hydrogenation of organics......Page 483
Electrocatalytic Reduction Of Carbon Dioxide......Page 484
Re(bpy)(CO)3Cl and related complexes......Page 485
[Ru(bpy)2(CO)2]2+ and related complexes......Page 486
Other polypyridyl metal complexes......Page 487
Porphyrin complexes......Page 488
Cyclam and other polyazamacrocyclic complexes......Page 489
Carboxylation of Organic Substrates......Page 490
Reductive homo- and heterocoupling of organic halides......Page 491
Electroreductive coupling of organic halides......Page 492
NiII and CoI Schiff base complexes......Page 493
NiII complexes of cyclams and other tetradentate N-ligands......Page 494
Vitamin B12 derivatives and model complexes......Page 495
Electrocatalytic Conversion of Nitrate to Ammonia......Page 496
Metal complexes of nitrogen macrocycles......Page 497
Electrochemical Sensors for Nitrite and Nitric Oxide Determination......Page 498
Electrocatalytic Four-electron Reduction of Dioxygen......Page 499
Electrocatalytic P-450 Model Systems......Page 501
The Gif-Orsay System......Page 502
Oxidation of Water......Page 503
Oxidation of Organics......Page 504
References......Page 506
Introduction......Page 514
Hydrolysis Reactions......Page 515
Heck Reactions......Page 517
Allylic Substitution......Page 519
Ring-closing Olefin Metathesis......Page 521
Olefin Polymerization......Page 523
Novel Strategies in the Design of Ligand Libraries......Page 527
Enantioselective Processes......Page 528
High-throughput ee-Assays......Page 529
Strategies Used in the Combinatorial Design and Preparation of Enantioselective Transition Metal Catalysts......Page 540
Conclusions and Perspectives......Page 550
References......Page 551
Introduction......Page 554
Nature of Bonding In Metal Complex Azo Colorants......Page 556
Azo/Hydrazone Tautomerism......Page 557
Nature of Azo-to-metal Bonding......Page 558
Lightfastness......Page 560
Color......Page 561
Azo Dyes......Page 562
Azo Pigments......Page 564
Phthalocyanine Dyes and Pigments......Page 565
Formazan Dyes......Page 566
Laser Printing Process......Page 568
Organic Photoconductors......Page 569
Toners......Page 571
Ink Jet Printing......Page 572
Ink Jet Printing Process......Page 573
Ink Jet Dyes and Pigments......Page 574
Infrared Absorbers......Page 577
Dark Oxidation Catalysts......Page 579
Singlet Oxygen Generators......Page 580
Toxicological And Ecotoxicological Considerations......Page 581
References......Page 582
Introduction......Page 585
Classes of Electrochromic Material......Page 586
Polypyridyl complexes in solution......Page 587
Oxidative electropolymerization of polypyridyl complexes......Page 588
Spatial electrochromism of polymeric polypyridyl complexes......Page 589
Sublimed bis(phthalocyaninato) lutetium(III) films......Page 590
Electrochemical routes to metallophthalocyanine electrochromic films......Page 592
Langmuir-Blodgett metallophthalocyanine electrochromic films......Page 593
Electrochromic properties of porphyrins......Page 594
Preparation of Prussian blue thin films......Page 595
Electrochemistry, in situ spectroscopy, and characterization of Prussian blue thin films......Page 596
Prussian blue electrochromic devices......Page 598
Prussian blue analogs......Page 599
Planar dithiolene complexes of Ni, Pd, and Pt......Page 601
Tris(pyrazolyl)borato-molybdenum complexes......Page 602
Ruthenium and osmium dioxolene complexes......Page 605
Read only media......Page 606
Write-once recordable media: CD-R and DVD-R......Page 609
Heat-mode recording......Page 611
Brief history of development of dyes for optical data storage......Page 612
Specific requirements for dyes for optical disk recording......Page 613
Phthalocyanines and related compounds......Page 614
Metal complexes of azo dyes......Page 618
References......Page 619
General Context and Scope of this Review......Page 624
The Origins of NLO Behavior in Molecular Materials......Page 625
Measurement of NLO Properties......Page 626
Why are Metal Complexes of Interest?......Page 629
Complexes of Nonchelating Pyridyl Ligands......Page 630
Complexes of Chelating Pyridyl Ligands......Page 635
Complexes of Porphyrin and Related Ligands......Page 641
Complexes of Phthalocyanine and Naphthalocyanine Ligands......Page 646
Complexes of Schiff Base Ligands......Page 653
Complexes of Thiocyanate Ligands......Page 658
Complexes of 1,2-Dithiolene and Related Ligands......Page 659
Cluster Complexes......Page 662
Miscellaneous Complexes......Page 670
Conclusions......Page 676
References......Page 678
9.15 Metal Compounds as Phosphors......Page 691
History of Phosphors and Past Uses......Page 692
Cathode Ray Tube Displays......Page 693
Electroluminescent Displays......Page 694
Field Emission Displays......Page 698
Phosphor Synthesis......Page 699
Homogeneous precipitation......Page 700
Microemulsion methods......Page 703
Molecular beam epitaxy and its derivatives......Page 704
Ion implantation......Page 705
Group II metal complexes......Page 706
Tris(8-hydroxyquinolato)aluminum and related complexes......Page 707
Lanthanide beta-diketonate complexes......Page 709
Other metal complexes......Page 710
Anti-Stokes Phosphors......Page 711
Quantum Cutters......Page 712
Photonics......Page 713
References......Page 714
9.16 Conversion and Storage of Solar Energy using Dye-sensitized Nanocrystalline TiO2 Cells......Page 720
Overview......Page 721
Operating Principles of the Dye-sensitized Solar Cell......Page 722
Fill Factor......Page 724
Photophysical Properties of Metal Complexes......Page 725
Preparation of Mesoscopic TiO2 Colloids......Page 726
Preparation of Films......Page 727
Requirements of the Sensitizers......Page 728
Spectral Tuning in \"Push-Pull\" Type Complexes......Page 729
Sensitizers Containing Functionalized Hybrid Tetradentate Ligands......Page 734
Hydrophobic Sensitizers......Page 736
Near IR Sensitizers......Page 738
Phthalocyanines containing 3d metals......Page 739
Surface Chelation......Page 741
X-ray Diffraction, X-ray Photoelectron Spectroscopy, and XAFS Spectroscopy Study......Page 742
ATR-FTIR Studies of Sensitizer Adsorption on TiO2 Oxide Surface......Page 743
Effect of Protons Carried by the Sensitizer on the Performance......Page 744
Comparison of IPCE Values Obtained with Various Sensitizers......Page 745
Electron Injection Kinetics......Page 747
New Redox Couples......Page 748
Solid Electrolytes/Hole-transport Materials......Page 749
Water Splitting by Visible Light using a Tandem cell......Page 750
Synthetic Strategies for Ruthenium Complexes......Page 751
Characterization......Page 753
Acknowledgements......Page 756
References......Page 757
Introduction......Page 760
Mineral Processing......Page 763
Leaching......Page 764
Leaching of Gold and Silver into Basic Media......Page 765
Leaching of Gold and Silver into Acidic Media......Page 766
Leaching of base metals into sulfate media......Page 767
Leaching of base metals into chloride media......Page 768
Separation And Concentration......Page 769
Solvent Extraction Processes......Page 770
Hydroxy-oxime Extractants......Page 771
Carboxylic Acids......Page 773
Amine Salt Extractants......Page 775
Solvating Extractants......Page 776
Extraction of CuII from sulfate solutions......Page 777
Extraction of CuII from chloride solutions......Page 779
Extraction of CuII from ammoniacal solutions......Page 781
Zinc......Page 782
Extraction of ZnII from sulfate media......Page 783
Extraction of ZnII from chloride media......Page 784
Nickel and Cobalt......Page 786
Co/Ni separation in sulfate solutions......Page 787
Co/Ni separation in chloride and ammoniacal solutions......Page 789
Precious Metals......Page 791
AuI, AuIII......Page 792
AgI......Page 794
PtIV, PtII......Page 795
PdII......Page 797
References......Page 798
Introduction......Page 810
Biological Assays......Page 811
Clinically Used Anticancer Agents. Cis-platinum Compounds......Page 813
AMD473 (ZDO-473)......Page 818
JM-216 (Satraplatin)......Page 819
BBR3464. A trinuclear platinum clinical agent......Page 820
Reactions with oligonucleotides......Page 822
Transplatinum compounds......Page 824
Ruthenium Complexes......Page 826
Arsenic Trioxide......Page 827
Manganese-based Superoxide Dismutase Mimics......Page 828
Titanium Compounds......Page 830
Silver and Mercury Salts......Page 831
Metal-containing Drugs as Antiparasitic Agents......Page 832
Lithium Carbonate......Page 833
Gold Compounds as Antiarthritic Agents......Page 834
References......Page 835
Introduction......Page 842
Relaxivity of GdIII Complexes......Page 844
Inner-sphere Proton Relaxivity......Page 846
Water/proton exchange......Page 848
Electron spin relaxation......Page 852
Toxicity of  GdIII Complexes: Thermodynamic Stability and Kinetic Intertness......Page 854
Complex Stability Constants......Page 855
Blood Plasma Models......Page 857
Blood Pool Agents......Page 858
Linear polymers......Page 859
Dendrimers......Page 860
Micelles and liposomes......Page 862
Noncovalently Bound Macromolecular Agents......Page 863
pH-sensitive Agents......Page 867
Temperature-sensitive Agents......Page 871
Enzymatically Responsive Contrast Agents......Page 872
Contrast Agents Responsive to Metal Ion Concentration......Page 874
Chemical Exchange Saturation (CEST) Contrast Agents......Page 875
Targeting Contrast Agents......Page 876
References......Page 878
Introduction......Page 883
Diagnostic Imaging......Page 884
Radiotherapy......Page 885
Nuclear and Physical Properties Needed for Imaging and Therapy......Page 886
Copper......Page 887
Radiolanthanides......Page 888
Rhodium......Page 889
Lead and Bismuth......Page 890
Gallium, Indium, and Yttrium......Page 891
Copper......Page 894
Radiolanthanides......Page 897
Gold......Page 902
Thallium......Page 903
Actinium......Page 904
Bismuth and Lead......Page 905
References......Page 906
Introduction and Scope......Page 912
Organic Molecules as Luminescent Probes for Metal Ions......Page 913
Lanthanide Complexes as Probes: Basic Photophysical Properties......Page 916
Long-lived Luminescence and Time-gating......Page 917
Sensitization of Luminescence: Energy Transfer......Page 918
Triplet-mediated energy transfer......Page 920
Energy transfer mediated by LMCT......Page 921
Solvent Effects on Lanthanide Luminescence......Page 922
Long-wavelength Sensitization and Near-IR Luminescence......Page 923
Background......Page 926
The DELFIA Assay......Page 929
The CYBERFLUOR Assay......Page 930
Homogeneous Assays: DEFRET......Page 933
Assays with Near-IR Luminescent Lanthanides......Page 934
Lanthanide Complexes for Imaging......Page 935
Responsive Lanthanide Complexes as Sensors......Page 938
References......Page 940
9.22 Metal Complexes for Photodynamic Therapy......Page 944
Introduction......Page 945
Mechanistic Aspects......Page 946
Design Features for a Good Photosensitizer for PDT......Page 949
Photosensitizers in Clinical Use......Page 952
Metalation of the preformed ligand......Page 954
Metal Complex Stability......Page 955
Solubility......Page 958
Disaggregation......Page 959
Spectroscopic Properties......Page 960
Redox Properties......Page 963
Drug Delivery Systems......Page 965
Magnesium......Page 966
Lanthanides......Page 969
Ruthenium......Page 971
Nickel......Page 972
Palladium......Page 974
Copper......Page 976
Porphyrin complexes......Page 978
Zinc chlorins and bacteriochlorins......Page 979
Zinc phthalocyanines......Page 980
Zinc naphthalocyanines......Page 983
Cadmium......Page 984
Boron......Page 985
Aluminum......Page 986
Gallium......Page 989
Silicon......Page 990
Germanium......Page 991
Tin......Page 992
Conclusions......Page 993
References......Page 994
9.23 Coordination Complexes as Precursors for Semiconductor Films and Nanoparticles......Page 1003
Compound Semiconductors......Page 1004
Thin Films from Vapor-phase Deposition Techniques......Page 1006
New Delivery Approaches......Page 1009
Coordination Chemistry Methods Used for Purification of Metal Alkyl Precursors: \"Adduct Purification\"......Page 1010
Purification of Group 12 Metal Alkyls......Page 1013
Purification of Group 13 Metal Alkyls......Page 1015
Modified Adduct Purification Techniques......Page 1017
Precursors for Fabrication of II-VI Thin Films......Page 1018
Precursors for Fabrication of III-V Thin Films......Page 1019
Aluminum Compounds......Page 1020
Gallium Compounds......Page 1021
Indium Compounds......Page 1022
Nitrogen Compounds......Page 1024
Arsenic Compounds......Page 1025
Dialkyldichalcogenocarbamato compounds......Page 1027
Lewis base adducts of bis(dialkyldithiocarbamato) compounds......Page 1029
Mixed alkyl/dichalcogenocarbamate complexes......Page 1030
Monothiocarbamate and monothiocarboxylate compounds......Page 1031
Chalcogenide-based compounds with high volatility......Page 1032
Single-molecule Precursors for III-V Compounds......Page 1035
Monomeric precursor compounds......Page 1037
Nitride Films from Single-molecule Precursors......Page 1038
Group 13 azides as single-molecule precursors for nitrides......Page 1039
III-VI Materials from Single-molecule Precursors......Page 1042
CuInS2 and Related Ternary Semiconductors......Page 1045
Semiconductor Nanoparticles \"Quantum Dots\"......Page 1046
Methods of Preparation of Semiconductor Nanoparticles......Page 1047
II-VI particles......Page 1049
III-V particles......Page 1051
References......Page 1054
9.24 Appendix to Volume 9......Page 1062