Comprehensive coordination chemistry II vol 9

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Comprehensive coordination chemistry II vol 9

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... Coordination Chemistry Volume 10: Cumulative Subject Index 10-Volume Set: Comprehensive Coordination Chemistry II COMPREHENSIVE COORDINATION CHEMISTRY II Volume 9: Applications of Coordination Chemistry. .. and Volume 6: Transition Metal Groups - 12 Volume 7: From the Molecular to the Nanoscale: Synthesis, Structure, and Properties Volume 8: Bio -coordination Chemistry Volume 9: Applications of Coordination. .. Monoxide 9. 1.8 OTHER LIVING COORDINATION POLYMERIZATIONS 9. 1.8.1 ROP of N-carboxyanhydrides and -lactams 9. 1.8.2 Polymerization of Isocyanates and Guanidines 9. 1 .9 REFERENCES 9. 1.1 54 57 58 58 58 59

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  • Cover Page

  • Introduction to Volume 9

  • COMPREHENSIVE COORDINATION CHEMISTRY II

  • Volumes

  • Info on Volume 9

  • Volume 9

    • 9.1 Metal Complexes as Catalysts for Polymerization Reactions

      • Introduction

      • Olefin Polymerization

        • Introduction

        • Catalyst Survey

          • Group 4 metallocene catalysts

            • Ethylene polymerization

            • Isospecific propylene polymerization

            • Syndiospecific propylene polymerization

            • Elastomeric poly(propylene)

          • Group 4 non-metallocenes

            • Constrained geometry catalysts

            • Nitrogen-based ligands

            • Oxygen based ligands

          • Group 3 and rare earth metal catalysts

          • Group 5 metal catalysts

          • Group 6 metal catalysts

            • Cyclopentadienyl systems

            • Nitrogen- and oxygen-based ligands

          • Group 8 metal catalysts

          • Group 9 metal catalysts

          • Group 10 metal catalysts

          • Main group metal catalysts

      • polymerization of Styrenes

        • Introduction

        • Coordinative Polymerization of Styrenes

        • Atom Transfer Radical Polymerization of Styrenes

      • Polymerization of Acrylates

        • Introduction

        • Anionic Initiators of the group 1, 2, and 3 Metals

        • Well-defined Magnesium and Aluminum Initiators

        • Lanthanide Initiators

        • Early Transition Metal Initiators

        • Atom Transfer Radical Polymerization

      • Ring-Opening Metathesis Polymerization of Cyclic Alkenes

        • Introduction

        • Titanacyclobutanes

        • Group 6 Metal Initiators

        • Ruthenium Initiators

        • Acyclic Diene Metathesis

      • Ring-Opening Polymerization of Cyclic Esters

        • Introduction

        • General Features of Lactone Polymerization

        • Aluminum-based Initiators

        • Zinc-Aluminum Oxo-alkoxide Initiators

        • Magnesium and Zinc Initiators

        • Calcium Initiators

        • Tin Initiators

        • iron Initiators

        • Yttrium and Rare-earth Initiators

        • Titanium and Zirconium Initiators

      • Ring-Opening Polymerization Of Epoxides

        • Introduction

        • Tetraphenylporphyrin Aluminum and Zinc Initiators

        • Non-porphyrinato Aluminum Initiators

        • Copolymerization of Epoxides and Aziridines with Carbon Monoxide

        • Copolymerization of Epoxides and Aziridines with Carbon Monoxide

      • Other Living Coordination Polymerizations

        • ROP of N-carboxyanhydrides and beta-lactams

        • Polymerization of Isocyanates and Guanidines

      • References

    • 9.2 Metal Complexes as Hydrogenation Catalysts

      • Introduction

      • Historical Background

      • Homogeneous Hydrogenation

        • Metal Monohydride Mechanism

        • Metal Dihydride Mechanism

        • Asymmetric Hydrogenation Mechanisms

      • Homogeneous Transfer Hydrogenation

        • Direct Hydrogen Transfer Mechanism

        • Metal Monohydride Mechanism

        • Metal Dihydride Mechanism

        • Metal-Ligand Bifunctional Concerted Mechanism

        • Mechanism of Aerobic Alcohol Oxidation

      • Homogeneous Hydrogenolysis

        • Hydrodesulfurization

        • Hydrodenitrogenation

      • New Developments in Hydrogenation

        • Hydrogenation in Aqueous Systems

          • Water-soluble hydrogenation catalysts

          • Immobilization on solids

          • Immobilization via biphasic catalysis

          • Microheterogenization on organized amphiphiles in the colloidal or nanoscale dimension

          • Enantioselective hydrogenation in aqueous systems

          • Transfer hydrogenation and hydrogenolysis in aqueous systems

          • Hydrogenations with CO/H2O mixtures

        • Hydrogenation in Supercritical Carbon Dioxide

        • Hydrogenation by Cluster Catalysis

      • Hydrogenation In Biological Systems

      • References

    • 9.3 Metal Complexes as Catalysts for Addition of Carbon Monoxide

      • Introduction

      • Carbonylation of Methanol

        • Rhodium Catalysts

          • Immobilization studies (see also Chapter 9.9)

        • Iridium Catalysts

        • Palladium and Nickel Catalysts

        • Cobalt Catalysts

        • Miscellaneous

          • Reductive carbonylation

          • Calculations

      • Hydroformylation

        • Platinum

          • Cis-PtCl2(PPh3)2SnCl2 systems

            • Studies on the mechanism of catalytic hydroformylation

            • The role of the trichlorostannyl ligand in the Pt-catalyzed hydroformylation

            • Cis-PtCl2(diphosphine)/SnCl2 systems

            • Miscellaneous

        • Palladium

        • Cobalt

        • Rhodium

          • Introduction to phosphine catalysts

          • Introduction to phosphite catalysts

        • Asymmetric Catalysis Using Platinum

          • Chiral diphosphine ligands

          • Aminophosphine-phosphinite ligands

          • Diphosphite ligands

          • Miscellaneous

        • Asymmetric Catalysis Using Rhodium

          • Diphosphines as chiral ligands

          • Diphosphite ligands

          • Phosphine-phosphite ligands

            • Miscellaneous

          • Two-phase catalysis

      • Palladium-Catalyzed Alternating Copolymerization of Alkenes And Carbon Monoxide

      • Reductive Carbonylation Of Nitro Compounds

        • Introduction

        • Ruthenium catalysts

        • Palladium catalysts

        • Rhodium catalysts

        • Amidocarbonylation

          • Palladium catalysts

          • Cobalt catalysts

      • Hydroxycarbonylation

        • Palladium/Phosphorus Complexes in Hydroxycarbonylation

        • Palladium Species Involved in the Hydroxycarbonylation Reaction

        • Methoxycarbonylation

          • Mechanistic studies

          • Palladium complexes involved in the methoxycarbonylation reaction

          • Phosphorus ligands in Pd methoxycarbonylation

          • Asymmetric methoxycarbonylation

      • References

    • 9.4 Metal Complexes as Catalysts for Oxygen, Nitrogen, and Carbon-atom Transfer Reactions

      • Introduction

      • Epoxidation

        • Epoxidation of Allylic Alcohols

        • Epoxidation of Isolated Olefins

          • Epoxidation using metalloporphyrin as catalysts

          • Epoxidation using metallosalen complexes as catalysts

        • Epoxidation of Electron-deficient Olefins

      • Oxidation of Enol Ethers and their Derivatives

      • Asymmetric Aziridination

      • Asymmetric Dihydroxylation

        • General Features of Asymmetric Dihydroxylation

        • Mechanistic Considerations

        • Models for the Enantiodifferentiating Step in Dihydroxylation

        • Iron-mediated Dihydroxylation

      • Asymmetric Aminohydroxylation

      • Asymmetric Cyclopropanation

        • Asymmetric Intermolecular Cyclopropanation

          • Cu-catalyzed cyclopropanation

          • Rh-catalyzed cyclopropanation

          • Ru-catalyzed cyclopropanation

          • Co-catalyzed cyclopropanation

        • Asymmetric Intramolecular Cyclopropanation

          • Cu-catalyzed cyclopropanation

          • Rh-catalyzed cyclopropanation

          • Ru-catalyzed cyclopropanation

          • Co-catalyzed cyclopropanation

        • Mechanism of Cyclopropanation

      • Conclusion

      • References

    • 9.5 Metal Complexes as Catalysts for H-X (X=B, CN, Si, N, P) Addition to CC Multiple Bonds

      • Introduction

      • Hydroboration

        • Developments Since CCC (1987)

        • Ligand Effects in Rhodium-catalyzed Hydroboration of Vinylarenes

        • Metal-catalyzed Hydroboration of Other C=C Bonds

        • Hydroboration of Substrates Containing C=C Bonds: Enynes and Alkynes

        • Asymmetric Hydroboration

      • Hydrocyanation

        • Reactions of Nonactivated Alkenes

        • Hydrocyanation of Activated Alkenes

      • Hydrosilylation

        • Developments in Achiral Catalytic Si-H Addition

        • Asymmetric Hydrosilylation

        • Enantioselective Hydrosilylation Employing Chiral Ferrocenyl Phosphine Ligands

        • Intramolecular Asymmetric Hydrosilylation

        • Enantioselective Hydrosilylation of C=O and C=N Bonds-A Brief Synopsis

      • Hydroamination

        • Mechanism and Early Transition Metal/Lanthanide Catalysts

        • Rhodium and Iridium Catalysts

        • Palladium and Platinum Catalysts

      • Hydrophosphination (And Hydrophosphorylation)

        • Hydrophosphination

        • Hydrophosphorylation and Hydrophosphinylation

      • References

    • 9.6 Metal Complexes as Catalysts for C-C Cross-coupling Reactions

      • Introduction

        • Notation used in examples

      • Major Methods of Cross-Coupling

        • Cross-coupling with Organoboron Compounds

        • Cross-coupling with Organotin Compounds

        • Cross-coupling with Organozinc Reagents

        • Cross-coupling with Organomagnesium and Organolithium Reagents

        • Cross-coupling with Terminal Acetylenes

      • The Development of the Cross-Coupling Methodology

        • Less Common Nucleophilic Reagents

          • Less common organometallics

            • Copper

            • Mercury

            • Aluminum

            • Gallium

            • Indium

            • Germanium

            • Titanium

            • Zirconium

            • Bismuth

            • Manganese

          • Electrochemical cross-coupling

          • CH-nucleophiles

        • Activation of Cross-coupling Reactions

          • Electrophilic catalysis

            • Copper

          • Activation of the nucleophilic reagent

          • Various activation methods in the cross-coupling of organosilicon compounds

            • Compounds with Si-O bonds

            • Tetraorganosilanes

            • Nonfluoride activation

        • Leaving Groups

          • Fluorides

          • Chlorides

          • Esters as electrophiles in cross-coupling reactions

          • Other neutral electrophiles

            • Sulfur derivatives

            • Se and Te derivatives

            • Organometallic compounds of main group metals

          • Diazonium salts

          • Iodonium salts

        • Catalysts

          • Monophosphine catalysis

          • Chelating ligands with both phosphine and nonphosphine binding sites

          • Bulky trialkyl- and dialkylphosphines

          • Bulky dialkylarylphosphines

          • Heterobimetallic complexes

          • Phosphorus ligands other than phosphines

          • Bidentate diphosphine ligands

          • Palladacycles

            • PC-Palladacycles

            • NC and OC-palladacycles

          • Nonphosphorus ligands

          • Heterocyclic carbene ligands

          • Palladium nanoparticles and "ligand-free" catalysis

        • Technological Aspects of Cross-coupling Chemistry

          • Microwave heating

          • Supported catalysts

            • Physical absorption on inorganic or similar supports

            • Pd/C and Ni/C

            • Polymer-immobilized catalysts

          • Aqueous systems

          • Fluorous systems

          • Supercritical CO2

          • Ionic liquids

      • References

    • 9.7 Metal Complexes as Catalysts for Carbon-heteroatom Cross-coupling Reactions

      • Introduction

      • Early Examples

      • Scope of the Reactions

        • Initial Intermolecular Tin-free Aminations of Aryl Halides

        • Second Generation Catalysts Bearing Aromatic Bisphosphines

          • Amination of aryl halides

          • Amination of aryl triflates

          • Amination of heteroaromatic halides

        • Third-generation Catalysts Bearing Alkylmonophosphines

          • Sterically hindered bisphosphine ligands for aminations

          • P,N, P,O, and dialkylphosphinobiaryl ligands

          • Low-temperature reactions catalyzed by P(t-Bu)3 complexes

          • Heterocyclic carbenes as ligands

          • Phosphine oxide ligands

        • Heterogeneous Catalysts

      • Aromatic C-N Bond Formation with Related Substrates

      • Etherification

        • Initial Studies with Arylphosphines

        • Second-generation Catalysts Containing Sterically Hindered Alkylphosphines

      • Carbon-Sulfur and Carbon-Selenium Bond-Forming Cross-Couplings

      • Carbon-Phosphorus Bond-Forming Cross-Couplings

        • Coupling of Aryl and Vinyl Halides with Phosphorus(V) Reagents

        • Coupling of Aryl and Vinyl Halides with Phosphorus(V) Reagents

      • Coupling of Aryl Halides with Silanes, Stannanes, Germanes, and Boranes

        • Coupling with Silanes, Stannanes, and Germanes

        • Coupling with Boranes

      • Intermediates in the Coupling Chemistry

      • References

    • 9.8 Metal Complexes as Lewis-acid Catalysts in Organic Synthesis

      • Introduction

      • Alkali Metals

      • Magnesium

      • Scandium and Lanthanides

      • Titanium

      • Zirconium

      • Hafnium

      • Copper

      • Silver and Gold

      • Zinc

      • Other Transition-Metal Lewis Acids

      • Boron

      • Aluminum

      • Silicon

      • Tin

      • Others

      • Conclusion/Classification of Lewis Acids

      • References

    • 9.9 Supported Metal Complexes as Catalysts

      • Introduction

      • The Different Procedures of Immobilization of Metal Complexes on Solid Supports

        • Introduction

        • Direct Reaction between the Solid Support and the Metal Complex

          • Inorganic supports

            • Incorporation by ion exchange reactions

            • Incorporation by covalent anchoring

          • Organic supports

            • Incorporation by ion exchange reactions

            • Incorporating by covalent bonding

        • Immobilization by Copolymerization

          • Inorganic matrices

          • Organic supports

        • Supported Liquid Phase Catalysts (SLPC)

      • Some Reactions Catalyzed By Supported Metal Complexes

        • Hydrogenation

        • Epoxidation

          • Supported titanium-based catalysts

          • Supported salen-type complexes

        • C-C Bond Formation by Cross Coupling

          • Heck reaction

          • Trost-Tsuji allylic substitution

        • Polymerization

      • Conclusion And Perspectives

      • References

    • 9.10 Electrochemical Reactions Catalyzed by Transition Metal Complexes

      • Introduction

      • Basic Principles

      • Electrocatalytic Reduction Of Protons And Hydride Transfer Reactions

        • Metal Hydride Complexes: Electrogeneration and Electrocatalytic Dihydrogen Evolution

          • Transition metal macrocycles

          • Polypyridyl complexes

          • Phosphine complexes

          • Miscellaneous complexes

        • Electrochemically Driven Hydride Transfer Reactions

          • Electrocatalytic regeneration of reduced nicotinamide cofactors

          • Electrocatalytic hydrogenation of organics

      • Electrocatalytic Reduction Of Carbon Dioxide

        • Polypyridyl Metal Complexes

          • Re(bpy)(CO)3Cl and related complexes

          • [Ru(bpy)2(CO)2]2+ and related complexes

          • Other polypyridyl metal complexes

        • Metal Complexes with Macrocycles

          • Phthalocyanine complexes

          • Porphyrin complexes

          • Cyclam and other polyazamacrocyclic complexes

        • Phosphine Complexes and Miscellaneous Complexes

          • Phosphine complexes

          • Other complexes

        • Carboxylation of Organic Substrates

      • Electrocatalytic Reduction Of Organic Halides

        • Polypyridyl Complexes

          • Reductive homo- and heterocoupling of organic halides

          • Carbonylation of organic halides

        • Phosphine Complexes

          • Electroreductive coupling of organic halides

          • Carbonylation and carboxylation of organic halides

        • Schiff Bases and Macrocyclic Nickel and Cobalt Complexes

          • NiII and CoI Schiff base complexes

          • NiII complexes of cyclams and other tetradentate N-ligands

          • Vitamin B12 derivatives and model complexes

      • Electrocatalytic Reduction of Dinitrogen and Nitrogen Oxides

        • Electrocatalytic Activation of Dinitrogen

        • Electrocatalytic Conversion of Nitrate to Ammonia

        • Electrocatalytic Reduction of Nitrite and Nitric Oxide

          • Metal complexes of nitrogen macrocycles

          • Polypyridyl complexes

          • Polyaminocarboxylate complexes

        • Electrochemical Sensors for Nitrite and Nitric Oxide Determination

      • Electrocatalytic Reduction and Activation of Dioxygen

        • Electrocatalytic Four-electron Reduction of Dioxygen

        • Electrocatalytic P-450 Model Systems

        • The Gif-Orsay System

      • Electrocatalytic Oxidation of Water and Organics

        • Oxidation of Water

        • Oxidation of Organics

      • References

    • 9.11 Combinatorial Methods in Catalysis by Metal Complexes

      • Introduction

      • Achiral Catalytic Processes

        • Hydrolysis Reactions

        • Hydrosilylation of Olefins and Imines

        • Heck Reactions

        • Hydroamination Reactions

        • Allylic Substitution

        • Annulation Reactions

        • Epoxidation Reactions

        • Ring-closing Olefin Metathesis

        • Reductive Aldol Addition

        • Olefin Polymerization

        • Novel Strategies in the Design of Ligand Libraries

      • Enantioselective Processes

        • High-throughput ee-Assays

        • Strategies Used in the Combinatorial Design and Preparation of Enantioselective Transition Metal Catalysts

      • Conclusions and Perspectives

      • References

    • 9.12 Metal Complexes as Speciality Dyes and Pigments

      • Introduction

      • Nature of Bonding In Metal Complex Azo Colorants

        • Azo/Hydrazone Tautomerism

        • Nature of Azo-to-metal Bonding

      • Effect Of Metallization on Properties

        • Lightfastness

        • Color

      • Textile And Related Applications

        • Azo Dyes

        • Azo Pigments

        • Phthalocyanine Dyes and Pigments

        • Formazan Dyes

        • Ortho-hydroxy Nitroso Dyes and Pigments

        • Others

      • Electrophotography (Laser Printing And Photocopying)

        • Laser Printing Process

        • Organic Photoconductors

        • Toners

      • Ink Jet Printing

        • Ink Jet Printing Process

        • Ink Jet Dyes and Pigments

      • Infrared Absorbers

      • Silver Halide Photography

      • Miscellaneous Applications

        • Dark Oxidation Catalysts

        • Singlet Oxygen Generators

        • Organic Semiconductors

      • Toxicological And Ecotoxicological Considerations

      • References

    • 9.13 Metal Complexes as Dyes for Optical Data Storage and Electrochromic Materials

      • Electrochromic Dyes

        • Introduction

        • Classes of Electrochromic Material

        • Electrochromism in Transition Metal Coordination Complexes

          • Electrochromism of polypyridyl complexes

            • Polypyridyl complexes in solution

            • Reductive electropolymerization of polypyridyl complexes

            • Oxidative electropolymerization of polypyridyl complexes

            • Spatial electrochromism of polymeric polypyridyl complexes

          • Electrochromism in metal phthalocyanines and porphyrins

            • Introduction to metal phthalocycanines and porphyrins

            • Sublimed bis(phthalocyaninato) lutetium(III) films

            • Other metal phthalocyanines

            • Electrochemical routes to metallophthalocyanine electrochromic films

            • Langmuir-Blodgett metallophthalocyanine electrochromic films

            • Species related to metal phthalocyanines

            • Electrochromic properties of porphyrins

          • Prussian blue systems

            • Prussian blue systems: history and bulk properties

            • Preparation of Prussian blue thin films

            • Electrochemistry, in situ spectroscopy, and characterization of Prussian blue thin films

            • Prussian blue electrochromic devices

            • Prussian blue analogs

          • Near-infrared region electrochromic systems

            • Significance of the near-infrared region

            • Planar dithiolene complexes of Ni, Pd, and Pt

            • Mixed-valence dinuclear complexes of ruthenium

            • Tris(pyrazolyl)borato-molybdenum complexes

            • Ruthenium and osmium dioxolene complexes

      • Metal Complexes as Dyes for Optical Data Storage

        • Background

        • Optical Data Storage Categories

          • Read only media

          • Write-once recordable media: CD-R and DVD-R

          • Rewriteable media

        • Optical Data Storage on Write-once Media

          • Heat-mode recording

          • CD-R: Recording mechanism

          • Brief history of development of dyes for optical data storage

          • Specific requirements for dyes for optical disk recording

          • Phthalocyanines and related compounds

          • Metal complexes of azo dyes

        • Future Developments

      • References

    • 9.14 Nonlinear Optical Properties of Metal Complexes

      • Introduction

        • General Context and Scope of this Review

        • The Origins of NLO Behavior in Molecular Materials

        • Requirements for NLO Activity

        • Measurement of NLO Properties

        • Why are Metal Complexes of Interest?

      • Coordination Complexes with Nlo Properties

        • Complexes of Nonchelating Pyridyl Ligands

        • Complexes of Chelating Pyridyl Ligands

        • Complexes of Porphyrin and Related Ligands

        • Complexes of Phthalocyanine and Naphthalocyanine Ligands

        • Complexes of Schiff Base Ligands

        • Complexes of Thiocyanate Ligands

        • Complexes of 1,2-Dithiolene and Related Ligands

        • Cluster Complexes

        • Miscellaneous Complexes

      • Conclusions

      • References

    • 9.15 Metal Compounds as Phosphors

      • Introduction

        • History of Phosphors and Past Uses

      • Current Uses Of Phosphors

      • Display Technologies Using Phosphors

        • Cathode Ray Tube Displays

        • Electroluminescent Displays

        • Vacuum Fluorescent Displays

        • Field Emission Displays

        • Plasma Displays

      • Phosphor Synthesis

        • Traditional Solid-state Synthesis

        • Hydrothermal and Related Methods

          • Homogeneous precipitation

          • Sol-gel methods

          • Microemulsion methods

        • Other Solution-based Techniques

          • Combinatorial methods

          • Solution-coating methods

        • Vapor-phase Methods

          • Chemical vapor deposition

          • Molecular beam epitaxy and its derivatives

          • RF magnetron sputtering

          • Electron beam evaporation

          • Pulsed laser decomposition

          • Ion implantation

          • Aerosol spray pyrolysis

          • Charged liquid cluster beam methods

      • Organo-Electroluminescent Devices

        • Coordination Compounds as Organo-electroluminescent Devices

          • Group II metal complexes

          • Tris(8-hydroxyquinolato)aluminum and related complexes

          • Lanthanide beta-diketonate complexes

          • Other metal complexes

        • Novel Organo-electroluminescent Devices/Inorganic Devices

        • Problems with Organo-electroluminescent Devices

      • Light-Emitting Diodes

      • Anti-Stokes Phosphors

      • Quantum Cutters

        • Novel Inorganic-Based Luminous Materials

      • Phosphorescent Paints

      • Photonics

      • The Future

      • References

    • 9.16 Conversion and Storage of Solar Energy using Dye-sensitized Nanocrystalline TiO2 Cells

      • Concepts and Definitions

        • Overview

        • Dye-sensitized Solar Cell

        • Dye-sensitized Solar Cell Fabrication

        • Operating Principles of the Dye-sensitized Solar Cell

        • Incident Photon-to-current Efficiency

        • Open-circuit Photovoltage

        • Fill Factor

        • Power Conversion Efficiency

        • Solar Radiation and Air Mass

        • Photophysical Properties of Metal Complexes

      • Semiconductor Films

        • Preparation of Mesoscopic TiO2 Colloids

        • Preparation of Films

      • Molecular Sensitizers

        • Requirements of the Sensitizers

        • Tuning of MLCT Transitions

        • Spectral Tuning in "Push-Pull" Type Complexes

        • Osmium Complexes

        • MLCT Transitions in Geometrical Isomers

        • Sensitizers Containing Functionalized Hybrid Tetradentate Ligands

        • Hydrophobic Sensitizers

        • Near IR Sensitizers

          • Ruthenium phthalocyanines

          • Phthalocyanines containing 3d metals

      • Surface Chelation and Electron Injection

        • Surface Chelation

        • X-ray Diffraction, X-ray Photoelectron Spectroscopy, and XAFS Spectroscopy Study

        • Acid-base Equilibria of cis-Dithiocyanato-bis(2,2'-bipyridine-4,4'-dicarboxylate) Ruthenium(II)

        • ATR-FTIR Studies of Sensitizer Adsorption on TiO2 Oxide Surface

        • Effect of Protons Carried by the Sensitizer on the Performance

        • Comparison of IPCE Values Obtained with Various Sensitizers

        • Electron Injection Kinetics

      • Redox Mediators

        • New Redox Couples

        • Solid Electrolytes/Hole-transport Materials

      • Energy Conversion and Storage

        • Water Splitting by Visible Light using a Tandem cell

      • Synthesis and Characterization of Complexes

        • Synthetic Strategies for Ruthenium Complexes

        • Purification

        • Characterization

      • Conclusions and Perspectives

      • Acknowledgements

      • References

    • 9.17 Metal Complexes for Hydrometallurgy and Extraction

      • Introduction

      • Mineral Processing

      • Leaching

        • Leaching of Gold and Silver into Basic Media

        • Leaching of Gold and Silver into Acidic Media

        • Leaching of Base Metals

          • Leaching of base metals into sulfate media

          • Leaching of base metals into chloride media

          • Leaching of base metals into ammoniacal media

      • Separation And Concentration

        • Solvent Extraction Processes

        • Hydroxy-oxime Extractants

        • Organophosphorus Acid Extractants

        • Carboxylic Acids

        • Amine Salt Extractants

        • Solvating Extractants

      • Base Metals

        • Copper

          • Extraction of CuII from sulfate solutions

          • Extraction of CuII from chloride solutions

          • Extraction of CuII from ammoniacal solutions

          • Recovery of CuII from secondary sources

        • Zinc

          • Extraction of ZnII from sulfate media

          • Extraction of ZnII from chloride media

          • Zn/Fe recovery from secondary sources

        • Nickel and Cobalt

          • Co/Ni separation in sulfate solutions

          • Co/Ni separation in chloride and ammoniacal solutions

      • Precious Metals

        • AuI, AuIII

        • AgI

        • PtIV, PtII

        • PdII

      • Conclusions

      • References

    • 9.18 Metal Complexes as Drugs and Chemotherapeutic Agents

      • Introduction

        • Biological Assays

      • Platinum Complexes As Therapeutic Agents

        • Clinically Used Anticancer Agents. Cis-platinum Compounds

        • Platinum Compounds in Clinical Trials

          • AMD473 (ZDO-473)

          • JM-216 (Satraplatin)

          • Poly (di and tri)-nuclear platinum complexes

            • BBR3464. A trinuclear platinum clinical agent

            • DNA binding of polynuclear platinum compounds

            • Aquation of dinuclear and trinuclear platinum agents

            • Reactions with oligonucleotides

            • Site-specific intrastrand and interstrand cross-links of BBR3464. Bending, protein recognition and nucleotide excision repair

          • Transplatinum compounds

      • Nonplatinum Anticancer Agents

        • Ruthenium Complexes

        • Arsenic Trioxide

        • The Mitochondrion as Target. Gold-phosphane Complexes

        • Manganese-based Superoxide Dismutase Mimics

        • Titanium Compounds

        • Gallium Nitrate

      • Antibacterial Agents

        • Silver and Mercury Salts

        • Bismuth-containing Antiulcer Drugs

        • Metal-containing Drugs as Antiparasitic Agents

      • Pharmacodynamic Uses of Metal Complex Drugs

        • Lithium Carbonate

        • Vanadium Complexes in Diabetes

        • Gold Compounds as Antiarthritic Agents

        • Nitric Oxide in Physiology and Medicine

        • Lanthanum Carbonate

      • References

    • 9.19 Metal Complexes as MRI Contrast Enhancement Agents

      • Introduction

      • Relaxivity of GdIII Complexes

        • Inner-sphere Proton Relaxivity

          • Hydration number and Gd-H distance

          • Water/proton exchange

          • Rotation

          • Electron spin relaxation

        • Outer and Second-sphere Relaxation

        • NMRD Profiles

      • Toxicity of GdIII Complexes: Thermodynamic Stability and Kinetic Intertness

        • Complex Stability Constants

        • Blood Plasma Models

        • Kinetic Inertness of GdIII Complexes

      • Blood Pool Agents

        • Covalently Bound Macromolecular Agents

          • GdIII chelates covalently bound to proteins

          • Linear polymers

          • Dendrimers

          • Dextran derivatives

          • Micelles and liposomes

        • Noncovalently Bound Macromolecular Agents

      • Smart Contrast Agents

        • pH-sensitive Agents

        • Temperature-sensitive Agents

        • Contrast Agents Sensitive to Partial Oxygen Pressure

        • Enzymatically Responsive Contrast Agents

        • Contrast Agents Responsive to Metal Ion Concentration

      • Chemical Exchange Saturation (CEST) Contrast Agents

      • Targeting Contrast Agents

      • References

    • 9.20 Radioactive Metals in Imaging and Therapy

      • Introduction

        • Diagnostic Imaging

        • Radiotherapy

        • Nuclear and Physical Properties Needed for Imaging and Therapy

      • Radionuclide Production

        • Cyclotron- or Accelerator-produced Radionuclides

          • Gallium

          • Copper

          • Tin

          • Rubidium

          • Thallium

        • Reactor-produced Radionuclides

          • Strontium

          • Yttrium

          • Radiolanthanides

          • Rhodium

          • Gold

          • Scandium

          • Actinium

          • Lead and Bismuth

      • Pharmaceutical Applications of Radionuclides

        • Gallium, Indium, and Yttrium

        • Copper

        • Radiolanthanides

        • Rhodium

        • Gold

        • Scandium

        • Tin

        • Thallium

        • Rubidium

        • Strontium

        • Actinium

        • Bismuth and Lead

      • Summary

      • Acknowledgement

      • References

    • 9.21 Fluorescent Complexes for Biomedical Applications

      • Introduction and Scope

      • Physical Background to Luminescence

      • Organic Molecules as Luminescent Probes for Metal Ions

      • Lanthanide Complexes as Probes: Basic Photophysical Properties

        • Long-lived Luminescence and Time-gating

        • Sensitization of Luminescence: Energy Transfer

          • Triplet-mediated energy transfer

          • Energy transfer mediated by LMCT

        • Solvent Effects on Lanthanide Luminescence

        • Long-wavelength Sensitization and Near-IR Luminescence

      • Lanthanide Complexes in Biological Assays

        • Background

        • The DELFIA Assay

        • The CYBERFLUOR Assay

        • Enzyme-amplified Lanthanide Luminescence (EALL)

        • Homogeneous Assays: DEFRET

        • Assays with Near-IR Luminescent Lanthanides

        • Use of Other Metal Ions in Assays

      • Lanthanide Complexes for Imaging

      • Responsive Lanthanide Complexes as Sensors

      • Conclusions

      • References

    • 9.22 Metal Complexes for Photodynamic Therapy

      • Introduction

      • Photodynamic Therapy

        • The Photodynamic Effect and Photodynamic Therapy

        • Mechanistic Aspects

        • Haematoporphyrin Derivative

      • Design Features for a Good Photosensitizer for PDT

      • Photosensitizers in Clinical Use

      • Coordination Complexes as PDT Sensitizers: Some General Considerations

        • Synthesis of Metalloporphyrins and Metallophthalocyanines

          • Metalation of the preformed ligand

          • Transmetalation

          • Template synthesis

        • Metal Complex Stability

        • Structural Variation

        • Solubility

        • Disaggregation

        • Spectroscopic Properties

        • Redox Properties

        • Drug Delivery Systems

      • Complexes of Group 2

        • Magnesium

      • Complexes of Group 3

        • Lanthanides

      • Complexes of Group 7

        • Manganese

        • Technetium

      • Complexes of Group 8

        • Ruthenium

      • Complexes of Group 10

        • Nickel

        • Palladium

        • Platinum

      • Complexes of Group 11

        • Copper

        • Gold

      • Complexes of Group 12

        • Zinc

          • Porphyrin complexes

          • Zinc chlorins and bacteriochlorins

          • Zinc phthalocyanines

          • Zinc naphthalocyanines

          • Other zinc complexes

        • Cadmium

      • Complexes of Group 13

        • Boron

        • Aluminum

        • Gallium

        • Indium

      • Complexes of Group 14

        • Silicon

        • Germanium

        • Tin

      • Conclusions

      • Acknowledgement

      • References

    • 9.23 Coordination Complexes as Precursors for Semiconductor Films and Nanoparticles

      • Introduction

        • Compound Semiconductors

        • III-V Materials

        • II-VI Materials

        • Thin Films from Vapor-phase Deposition Techniques

        • Precursor Volatility by Molecular Design

        • New Delivery Approaches

        • Related Deposition Techniques

      • Coordination Chemistry Methods Used for Purification of Metal Alkyl Precursors: "Adduct Purification"

        • Purification of Group 12 Metal Alkyls

        • Purification of Group 13 Metal Alkyls

        • Modified Adduct Purification Techniques

      • Precursors for Fabrication of II-VI Thin Films

        • New Group 12 Precursors

        • New Group 16 Precursors

      • Precursors for Fabrication of III-V Thin Films

        • Aluminum Compounds

        • Gallium Compounds

        • Indium Compounds

        • Nitrogen Compounds

        • Phosphorus Compounds

        • Antimony Compounds

        • Arsenic Compounds

      • Single-Molecule Approach to the Deposition of Compound Semiconducting Materials by Mocvd

        • Single-molecule Precursors for II-VI Materials

          • Dialkyldichalcogenocarbamato compounds

          • Asymmetric dialkyldichalcogenocarbamato precursors

          • Lewis base adducts of bis(dialkyldithiocarbamato) compounds

          • Mixed alkyl/dichalcogenocarbamate complexes

          • Mixed alkyl/dichalcogenocarbamate complexes as precursors for ternary materials

          • Monothiocarbamate and monothiocarboxylate compounds

          • Other chalcogenide-based compounds

          • Chalcogenide-based compounds with high volatility

          • Thiophosphinates and related compounds

        • Single-molecule Precursors for III-V Compounds

          • Dimeric precursor compounds

          • Monomeric precursor compounds

          • Trimeric precursor compounds

        • Nitride Films from Single-molecule Precursors

          • Group 13 azides as single-molecule precursors for nitrides

        • III-VI Materials from Single-molecule Precursors

        • IV-VI Materials from Single-molecule Precursors

        • CuInS2 and Related Ternary Semiconductors

      • Preparation of Nanodimensional Materials Using Single-Molecule Precursors

        • Semiconductor Nanoparticles "Quantum Dots"

        • Methods of Preparation of Semiconductor Nanoparticles

        • Semiconductor Nanoparticles Produced from Single-molecule Precursors

          • II-VI particles

          • III-V particles

          • II-V particles

          • III-VI particles

      • References

    • 9.24 Appendix to Volume 9

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