Phosphazenes: A Worldwide Insight

3.4 Reversibility of the Reaction

3.5 Molecular Weight Regulation

3.6 Catalysis of the Reaction

4. MOLECULAR WEIGHTS DETERMINATION

5. STABILIZATION OF POLY(DICHLOROPHOSPHAZENE)

6. EXPERIMENTAL PROCEDURE

7. CONCLUSION

ACKNOWLEDGMENTS

REFERENCES

Chapter 3: AMBIENT TEMPERATURE CATIONIC CONDENSATION SYNTHESIS OF POLYPHOSPHAZENES

OVERVIEW

SYNTHESIS OF POLY(DICHLOROPHOSPHAZENE)

Background 1: The Ring-Opening Polymerization Route

Background 2: Phosphoranimine-Based Syntheses

Monomer Synthesis and Purity

Polymerization Initiators

Effects of Solvents and Temperature

Molecular Weight Control and Sequential Chain Building

Star-Geometry Polymers

APPLICATION OF THE LIVING CATIONIC METHODTO ORGANO-HALOGENO PHOSPHORANIMINES

Overall Principles

PHOSPHAZENE-PHOSPHAZENE BLOCK COPOLYMERS

TELECHELIC POLYPHOSPHAZENES AND FORMATION OF BLOCKCOPOLYMERS WITH CLASSICAL ORGANIC MACROMOLECULES

EXAMPLES OF THE USE OF TELECHELIC POLYPHOSPHAZENES TOPRODUCE BLOCK COPOLYMERS WITH ORGANIC MACROMOLECULES

GRAFT COPOLYMERS

FINAL COMMENTS

ACKNOWLEDGMENTS

REFERENCES

Chapter 4: SOME ASPECTS OF SYNTHESIS AND INVESTIGATION OF POLY(DIORGANOXYPHOSPHAZENE)S

1. INTRODUCTION

2. SYNTHESIS AND STUDIES OF POLYDICHLOROPHOSPHAZENE

2.1. Effect of Higher Cyclic Chlorophosphazene onHexachlorocyclotriphosphazene Polymerization

2.2. Effect of Water and HCl on HexachlorocyclotriphosphazenePolymerization

2.3. Properties of Polydichlorophosphazene in Solution

3. MULTIFRAGMENTARITY OF POLY(DIORGANOPHOSPHAZENE)S

4. SYNTHESIS OF POLY(DIORGANOXYPHOSPHAZENE)S

4. 1. Synthesis of Polyalkoxyphosphazenes

4.2. Synthesis of Polyaryloxyphosphazenes

5. SYNTHESIS OF POLY(DIORGANOXYPHOSPHAZENE)SWITH MIXED SUBSTITUENTS

5.1. Synthesis of Thermally Resistant Poly(diaryloxyphosphazene)s withSpirocyclic Groups

5.2. Other Possibilities of Synthesis of Poly(diorganoxyphosphazene)swith Mixed Substituents

REFERENCES

Chapter 5: POLY(ALKYL/ARYLPHOSPHAZENES) AND THEIR DERIVATIVES

SUMMARY

INTRODUCTION

CONDENSATION POLYMERIZATION OF N-SILYLPHOSPHORANIMINES

MODIFICATION OF PREFORMED POLY(ALKYL/ARYLPHOSPHAZENES)

CHARACTERIZATION AND PROPERTIES

REFERENCES

Chapter 6: P-C BONDED POLYPHOSPHAZENES

ABSTRACT

INTRODUCTION

1. SYNTHETIC FEATURES FOR ALKYL- AND/ORPHENYLPHOSPHAZENE POLYMERS

1.1. Polydimethylphosphazene

1.2. Polydiethylphosphazene

1.3. Polydipropylphosphazene

1.4. Polydihexylphosphazene

1.5. Copolymers and Functional Group Insertion

2. STRUCTURE, AND CHEMICAL AND PHYSICAL PROPERTIESOF POLY-ALKYL, AND/OR -PHENYLPHOSPHAZENES

2.1. Polydimethylphosphazene

2.2. Polydiethylphosphazene

2.3. Polydipropylphosphazene

3. CYCLIC ALKYL-, AND/OR ARYLPHOSPHAZENE OLIGOMERS

4. ELECTRON DONOR PROPERTIES OF THE P=NREPEATING UNIT IN PHOSPHAZENES

5. TECHNOLOGICAL APPLICATIONS

5.1. Separation Membranes

5.2. Humidity Sensors

5.3. Gas Chromatographic Stationary Phases

5.4. Proton Conducing Electrolytes

REFERENCES

Chapter 7: HYBRID INORGANIC-ORGANIC PHOSPHAZENE POLYMERS

1. INTRODUCTION

2. LINEAR POLYMERS WITHPENDANT CYCLOPHOSPHAZENE GROUPS

2.1. Synthesis of Precursors for Radical Polymerization

2.2. Radical Polymerization and Reactivity

2.3. Synthesis by Condensation Polymerization, ROMP and Hydrosilylation

3. CYCLOLINEAR AND CYCLOMATRIX POLYMERS

4. CONCLUSIONS

5. REFERENCES

Chapter 8: HIGH MOLECULAR WEIGHT POLYSPIROPHOSPHAZENES

1. INTRODUCTION

2. CYCLIC SPIROPHOSPHAZENE MODELS

3. SPIROPHOSPHAZENE HIGH MOLECULAR WEIGHT POLYMERS

3.1. Ring Opening Polymerization of Spirocyclophosphazenes (2 in Scheme 2)

3.2. Condensation Polymerization of Cyclic Precursors (3 in Scheme 2)

3.3. Nucleophilic Substitution Reactions (Reaction 1 in Scheme 2)

4. THE PROPERTIES OF POLYSPIROPHOSPHAZENES

4.1. Thermal Stability

4.2. Glass Transition Temperatures (Tg)

4.3. Solution Properties

4.4. Spectroscopic Properties

4.5. Rheological Studies

5. APPLICATIONS

ACKNOWLEDGMENTS

REFERENCES

Chapter 9: POLYTHIONYLPHOSPHAZENES: INORGANIC POLYMERS WITH A MAIN CHAIN OFPHOSPHORUS, NITROGEN AND SULFUR(VI) ATOMS

1. INTRODUCTION

2. CYCLIC THIONYLPHOSPHAZENE MONOMERS

3. THERMAL ROP OF CYCLIC THIONYLPHOSPHAZENES

4. ISOLATION OF MACROCYCLES FROM THERMAL ROP MIXTURES

5. SYNTHESIS AND PROPERTIES OF HYDROLYTICALLY-STABLEPOLYTHIONYLPHOSPHAZENES

6. APPLICATIONS OF POLYTHIONYLPHOSPHAZENESAS MATRICES FOR OXYGEN SENSORS

7. AMBIENT TEMPERATURE SYNTHESIS OFPOLYTHIONYLPHOSPHAZENES VIA ROP

8. CONDENSATION ROUTES TO SULFURNITROGEN-PHOSPHORUS POLYMERS

9. SUMMARY

REFERENCES

PART 2. CHARACTERIZATION OF POLYPHOSPHAZENES

Chapter 10: SOLUTION PROPERTIES OF POLYPHOSPHAZENES DETERMINED BY SEC-MALS AND CALCULATED BY MD SIMULATIONS

ABSTRACT

INTRODUCTION

THEORY

RESULTS AND DISCUSSION

Calibration Curves

Molecular Weight Distributions

Scaling Laws

Unperturbed Dimensions

Solution Properties below Theta Temperature

THEORETICAL CALCULATIONS

ACKNOWLEDGEMENT

REFERENCES

Chapter 11: COMPUTATIONAL APPROACHES TOTHE STUDY OF STRUCTURES ANDCONFORMATIONS OF SEMI-CRYSTALLINE ANDAMORPHOUS PHOSPHAZENIC MATERIALS

SUMMARY

SCOPE OF THIS REVIEW

1. COMPUTATIONAL TOOLS

1.a. Quantum Mechanical Methods

1.b. Molecular Mechanics

1.c. Molecular Simulations

2. COMBINED COMPUTATIONAL - EXPERIMENTAL APPROACH

ACKNOWLEDGMENT

REFERENCES

Chapter 12: THERMAL AND MECHANICAL PROPERTIES OF POLYPHOSPHAZENES

1. INTRODUCTION

2. THERMAL PROPERTIES

2.1 Poly(aryloxy)phosphazenes

2.2 Poly(alkoxy)phosphazenes

2.3 Poly(alkyl and aryl) Phosphazenes

2.4 Poly(amino)phosphazenes

2.5 Relationship between Tg and Te

3. MECHANICAL PROPERTIES

4. DYNAMIC MECHANICAL PROPERTIES

REFERENCES

Chapter 13: CRYSTALLIZATION OF POLYPHOSPHAZENES

INTRODUCTION AND BACKGROUND

Phase Transitions Methods for Polyphosphazenes

RELATIONSHIPS BETWEEN BASIC PHASE PARAMETERS

Crystallization from Solution

OPTICAL MICROSCOPE TRANSFORMATIONS

Fiber-Forming Behavior from Concentrated Solutions

SYNCHROTRON RADIATION MEASUREMENTS

P NMR Variable Temperature Measurements

Differential Scanning Calorimetry

LIGHT TRANSMISSION (DLI) TECHNIQUE

Dilatometric Measurements

Thermo-mechanical and Dielectric Phase Transition

Creep-Temperature Scans of Transitions

CONCLUSIONS

REFERENCES

APPENDIX I

Chapter 14: ELECTROCHEMICAL BEHAVIOUR OF PHOSPHAZENES AND THEIR COMPLEXES

1. INTRODUCTION

2. PHOSPHAZENES

3. CYCLIC PHOSPHAZENES

3.1. Cathodic Behaviour

3.2. Anodic Behaviour

3.3. ESR Studies

4. TRANSITION METAL PHOSPHAZENE COMPLEXES

4.1. Ferrocenyl Compounds

4.2. Phosphazenes Bearing Nitrile Coordinating Groups

4.3. Phosphazenes Bearing Pyrazolyl Derived Groups

4.4. Cyclometallaphosphazenes

5. POLYPHOSPHAZENES

5.1 Polyphosphazenes with Pendent Organic Groups

5.2 Polyphosphazenes with Transition-Metal Side Groups

6. FINAL COMMENTS

ACKOWLEDGEMENTS

REFERENCES

PART 3. APPLICATIVE ASPECTS OF POLY(ORGANOPHOSPHAZENES)

Chapter 15: BIODEGRADABLE POLYPHOSPHAZENES FOR BIOMEDICAL APPLICATIONS

1. INTRODUCTION

2. SYNTHESIS OF POLY[(DICHLORO)PHOSPHAZENE]

2.1. Synthesis by Ring-Opening Polymerisation

2.2. Synthesis by Polycondensation

2.3. Synthesis by Polymerisation of Phosphoranimines

3. BIODEGRADABLE POLYPHOSPHAZENES

3.1. Polyphosphazenes having Amino Acid Ester Side Groups

3.2. Imidazolyl-Substituted Polyphosphazenes

3.3. Glyceryl and Glucosyl Containing Polymers

3.4. Glycolate and Lactate Substituted Polyphosphazenes

3.5. Other Biodegradable Polyphosphazenes

4. POLYPHOSPHAZENES USED IN DRUG DELIVERY SYSTEMS

4.1. Covalent Polymer-Drug Combinations

4.2. Physical Polymer-Drug Combinations

5. USE OF POLYPHOSPHAZENES IN TISSUE ENGINEERING

6. GENERAL CONCLUSIONS

7. ACKNOWLEDGMENT

REFERENCES

Chapter 16: USES OF POLYPHOSPHAZENE IN DENTISTRY

MATERIALS SCIENCE AND DENTISTRY

TOOTH LOSS AND PROSTHESES

RESILIENT OR SOFT DENTURE LINERS

CANDIDATE ELASTOMERS

CHOICE OF POLYPHOSPHAZENE

FINAL DENTURE LINER COMPOSITION

INTERPENETRATING NETWORKS

PHYSICAL PROPERTIES

BIOLOGICAL TESTING

LABORATORY PROCESSING

CLINICAL TRIALS

U.S. FOOD & DRUG ADMINISTRATION APPROVAL

MARKETING

OBTAINING ETHYL􀂶S EYPEL®-F

COMPOUNDING

WITHDRAWAL OF ETHYL􀂶S EYPEL®-F

FUTURE USES OF POLYPHOSPHAZENES

REFERENCES

Chapter 17: PHOSPHAZENES AND LIGHT

INTRODUCTION

LIGHT-INDUCED DEGRADATION PHENOMENA INPOLY(ORGANOPHOSPHAZENES)

PHOTOCROSSLINKING PROCESSES IN PHOSPHAZENES

LIGHT-INDUCED GRAFTING REACTIONS IN PHOSPHAZENES

PHOSPHAZENE-BASED PHOTORESISTS

PHOTOCONDUCTIVITY IN POLYPHOSPHAZENES

MISCELLANEOUS PHOSPHAZENE-LIGHT INTERACTIONS

PHOTOPHYSICS OF PHOSPHAZENES

CYCLOPHOSPHAZENES IN PHOTOCHEMISTRY

CONCLUSION

REFERENCES

Chapter 18: RADIATION CHEMISTRY OF POLYPHOSPHAZENES: FUNDAMENTALS AND APPLICATIONS

ABSTRACT

INTRODUCTION

POLYMERIZATION

RADIOLYSIS OF POPS

APPLICATIONS OF POPS IN BIOMEDICINE

OTHER APPLICATIONS

REFERENCES

Chapter 19: PHOSPHAZENE HYBRIDS BY SOL-GEL

SUMMARY

INTRODUCTION

SHORT INTRODUCTION TO THE SOL-GEL TECHNIQUE

SYNTHESIS OF CYCLO- AND POLY-PHOSPHAZENES

SYNTHESIS OF PHOSPHAZENE/INORGANICMATRIX HYBRID MATERIALS

PROPERTIES AND PRACTICAL APPLICATIONS OFPHOSPHAZENE/INORGANIC MATRIX HYBRID MATERIALS

Thermally Stable Materials

Phosphazene/Silica Hybrids with Improved Mechanical Properties

Polyphosphazene Hybrids as Ionic Conductors

PHOSPHAZENE POLYMERS AS COLORED COATINGS

POPOH/SIO2 HYBRID MATERIALSUNDER HIGH ENERGY IRRADIATION

PHOSPHAZENE HYBRIDS FOR BIOMEDICAL APPLICATIONS

PHOSPHAZENE HYBRID MATERIALSAS GAS SEPARATION MEMBRANES

CONCLUSION

REFERENCES

Chapter 20: THE USE OF PHOSPHAZENESAS FLAME RETARDANTS

I. INTRODUCTION

A. Problems Associated with Commercial Flame Retardants

B. Fire and Fire Retardancy

C. Evaluation of Flame Retardants

D. Fundamentals of Commercial Nitrogen-PhosphorusBased Flame Retardants

E. Classes of Phosphazenes Exhibiting Flame Retardancy

II. PHOSPHAZENES AS ADDITIVES

A. Cyclophosphazenes

B. Polymeric Additives

III. PHOSPHAZENES AS INHERENTLYFLAME RETARDANT MATERIALS

A. Small Molecule Species

B. Polymers with Cyclophosphazenes as Substitutents

C. Cyclolinear Phosphazenes

D. Cyclomatrix Phosphazenes

E. Polyphosphazenes

IV. CONCLUSIONS

REFERENCES

Chapter 21: POLYPHOSPHAZENE BLENDS

SUMMARY

INTRODUCTION

Polyphosphazene Blends with Organic Polymers

Research in Phosphazene Compatibilization Processes

Flame Retardant Phosphazene Blends

Blends for Dimensional Stabilization

Phosphazene Blends to Improve Ionic Conductivity of PEO

Phosphazene Blends for Biomedical Applications

Phosphazene Blends for Membrane Separation Processes

Other Phosphazene/Organic Polymer Blends

BLENDS BETWEEN POLYPHOSPHAZENES AND INORGANIC POLYMERS

BLENDS BETWEEN DIFFERENTLY SUBSTITUTEDPOLY(ORGANOPHOSPHAZENES)

CROSSLINKING AND REACTIVE BLENDING PROCESSES

CYCLOPHOSPHAZENES AS MODIFIERS FOR MACROMOLECULES

CONCLUSION

REFERENCES

LIST OF ABBREVIATIONS

Chapter 22: IONICALLY CONDUCTIVE PHOSPHAZENE POLYMERS

INTRODUCTION

1. LINEAR POLYPHOSPHAZENES WITH PENDANT DONOR ATOMS

1.1 Polyphosphazenes with Oligo(Ethyleneoxy) Side Groups

1.2. Poly(Phosphazene)-Based Single Ion Conductor

1.3 Modified Linear Polyphosphazenes with Oligo(Ethyleneoxy) Side Chains

2. POLYELECTROLYTES WITH PENDANTOLIGO(ETHYLENEOXY)CYCLOTRIPHOSPHAZENES

3. POLYELECTROLYTES WITH PHOSPHAZENE CORE

CONCLUSION

REFERENCES

Chapter 23: POLYPHOSPHAZENE MEMBRANES

ABSTRACT

INTRODUCTION

RECENT PROGRESS IN THE PREPARATION OF PHOSPHAZENES,PHOSPHAZENE BASED MATERIALS AND PHOSPHAZENE MEMBRANES

Gas Separation (GS)

Pervaporation (PV) and Vapor Permeation (VP)

Ultrafiltration and Nanofiltration

PERSPECTIVES

CONCLUSIONS

ACKNOWLEDGEMENTS

REFERENCES

Chapter 24: LINEAR AND CYCLOMATRIX POLYPHOSPHAZENE RESEARCH FOR MEMBRANE APPLICATIONS

INTRODUCTION

LINEAR PHOSPHAZENE POLYMERS WITH IMPROVED PROPERTIES

SOLUBLE CYCLOMATRIX POLYPHOSPHAZENES

ACKNOWLEDGEMENTS

REFERENCES

Chapter 25: SULFONATED POLYPHOSPHAZENE MEMBRANES FOR DIRECT METHANOL FUEL CELLS

1. INTRODUCTION

1.1 Improving the Performance of Direct Liquid Methanol PEM Fuel Cellswith Polyphosphazenes

2. MEMBRANE PREPARATION

2.1 Polyphosphazene Sulfonation

2.2 Polyphosphazene Crosslinking

2.3 Blending and Crosslinking Sulfonated Polyphosphazenes

3. MEMBRANE CHARACTERIZATION AND TESTING

3.1 Proton Conductivity

3.2 Water Diffusion Coefficient Measurements

3.3 Methanol Crossover Measurements

3.4 Chemical Stability and Mechanical Properties

3.5 Preliminary Direct Methanol Fuel Cell Experiments

ACKNOWLEDGEMENTS

REFERENCES

Chapter 26: POLYORGANOPHOSPHAZENE METAL CATALYSTS

INTRODUCTION

POLYORGANOPHOSPHAZENE RUTHENIUM CATALYSTS

POLYORGANOPHOSPHAZENE RHODIUM CATALYSTS

POLYORGANOPHOSPHAZENE PALLADIUM CATALYSTS:PREPARATION AND CATALYTIC ACTIVITY IN THE HECK REACTION

ACKNOWLEDGEMENTS

REFERENCES

Chapter 27: SYNTHESIS AND APPLICATIONS OF PHOSPHAZENE COMPOUNDS

1. INTRODUCTION

2. PHOSPHAZENE POLYMERS

2.1 Electrical Conductivity

2.2 Gas Permeability and Selectivity

2.3 Oxygen Gas Permeability in Water

2.4. Cultivation Bed

2.5 Microlithography

2.6 Liquid Crystalline Behavior of Phosphazene Polymers

3. PHOSPHAZENE OLIGOMERS

3.1 Cross-Linking Agents

3.2 Flame Retardants

3.3 Electrical Conductivity

3.4 Adhesive Properties

3.5 Non-flamable Electrolyte for Lithium Battery

3.6 LIQUID CRYSTALLINE STATE OF PHOSPHAZENE OLIGOMERS

3.6.1 Cyclotriphosphazene Derivatives

3.6.2 Cyclotetraphosphazene Derivatives

3.6.3 The Comparison of Phase Transition in Cyclotriphosphazene andCyclotetraphosphazene

REFERENCES

PART 4. APPLICATIVE ASPECTS OFCYCLOPHOSPHAZENES

Chapter 28: CYCLOPHOSPHAZENES AS HYDRAULICFLUIDS, LUBRICANTS AND ADDITIVES

SUMMARY

INTRODUCTION

SYNTHESIS AND CHARACTERIZATION OFCYCLOPHOSPHAZENE HYDRAULIC FLUIDS

Synthesis of Cyclophosphazene Hydraulic Fluids

Characteristics of Cyclophosphazene Hydraulic Fluids

CYCLOPHOSPHAZENES LUBRICANTS FOR MAGNETIC APPLICATIONS

Cyclophosphazene Lubricants for Magnetic Recording Media

Cyclophosphazenes as Additives for PFPE Lubricants for MagneticRecording Media

Toxicity of Cyclophosphazene Hydraulic Fluids

CONCLUSIONS

REFERENCES

Chapter 29: STAR POLYMERS WITH CYCLOTRIPHOSPHAZENE CORES

INTRODUCTION

SYNTHESIS OF MULTIFUNCTIONAL CYCLOTRIPHOSPHAZENES

RING OPENING POLYMERIZATION

ATOM TRANSFER RADICAL POLYMERIZATION

COUPLING REACTION OF THE REACTIVE POLYMERS WITHMULTIFUNCTIONAL CYCLOTRIPHOSPHAZENES

REFERENCES

Chapter 30: SYNTHESIS, REACTIVITY, PROPERTIES ANDAPPLICATIONS OF DENDRIMERS BUILT FROMCYCLOPHOSPHAZENE CORES

I. INTRODUCTION

II. SYNTHESIS OF DENDRIMERS FROM CYCLOPHOSPHAZENE CORES

III. REACTIVITY ON THE SURFACE OF DENDRIMERS

IV. REACTIVITY OF THE INTERNAL LAYERS OF DENDRIMERS

V. PROPERTIES AND APPLICATIONS

VI. CONCLUSION

VII. REFERENCES

Chapter 31: CONSTRUCTION AND FUNCTIONALITY OF SUPRAMOLECULES BASED ON CYCLOTRIPHOSPHAZENES

INTRODUCTION

HOST-GUEST COMPLEXES BASED ON CYCLOTRIPHOSPHAZENES

SELF-ASSEMBLY OF CYCLOTRIPHOSPHAZENE DERIVATIVES

STAR POLYMERS AND DENDRIMERS BASED ONCYCLOTRIPHOSPHAZENES

SELF-ORGANIZATION IN LIQUID CRYSTAL PHASES

SUMMARY

REFERENCES

Chapter 32: UNIQUE SYNTHETIC OPPORTUNITIES ON THE BORDERLINE OF CYCLOPHOSPHAZENE CHEMISTRY AND SUPRAMOLECULAR CHEMISTRY

1. SCOPE OF THE CONTRIBUTION

2. INTRODUCTION TO SUPRAMOLECULAR CHEMISTRY

3. SUPRAMOLECULAR SYNTHESIS OFCYCLOPHOSPHAZENIC SELF-ASSEMBLIES

4. GENERAL CONSIDERATIONS ON MACROCYCLIC LIGANDS BASED ON THE CYCLOPHOSHAZENE SKELETON AS A CORE

5. CYCLOPHOSPHAZENIC POLYPODANDS

6. INTRODUCTION TO THE SUBJECT OFCYCLOPHOSPHAZENE MACROCYCLES

7. THE REACTIONS OF CHLOROCYCLOPHOSPHAZENESWITH DIFUNCTIONAL REAGENTS

7.1. Ansa Derivatives

8. SUPRAMOLECULAR ASSISTANCE TO REGIOSELECTIVITY IN THEREACTIONS OF FUNCTIONAL PNP-CROWN ETHER 2 WITH CATIONPAIREDOXYANIONS AND AMINO-COMPOUNDS

8.1. Reactions of Tetrachloro-PNP-Crown 2 with Ion-Paired OxyNucleophiles

8.2. Reactions of the PNP-Crown 2 with Aliphatic Diamines

9. ARYLOXY AND AMINO-SUBSTITUTED DERIVATIVES OF PNPCROWN2 AS COMPLEXING LIGANDS OF LARIAT ETHER TYPE

9.1. Introduction

9.2. Preliminary Screening of Complexation Properties of the PNP-LariatEthers

9.3. Structure-Property Relationships of Tetrapyrrolidinyl PNP-Lariat Ether28 and its Complexes with Potassium, Sodium and Silver Cations

9.4. Conclusions

10. THE RECONNAISSANCE STUDIES ON THE POSSIBLE APPLICATIONOF THE PNP-CROWN DERIVATIVES IN CANCER CHEMOTHERAPY

11. SUMMARY

REFERENCES

Chapter 33: CROWN ETHER BEARING PHOSPHAZENES

I. INTRODUCTION

II. CROWN ETHER BEARING POLYPHOSPHAZENES

II.1. Crown Ether Single-Substitutent Polyphosphazenes

II. 2. Crown Ether Co-Substituted Polyphosphazenes

III. CROWN ETHER BEARING CYCLOTRIPHOSPHAZENE

III. 1. Syntheses

III. 2. Complexation Studies of Compound 21

IV. CONCLUSION

REFERENCES

Chapter 34: COORDINATION CHEMISTRY OF CYCLOPHOSPHAZENES

INTRODUCTION

IONIC SALTS

COORDINATION BY THE SKELETAL NITROGENATOMS OF THE CYCLOPHOSPHAZENE RING

Effect of Protonation or Ring Nitrogen Coordination Upon theCyclophosphazene Ring

RING PHOSPHORUS INTERACTION

CYCLOPHOSPHAZENE LIGANDS CONTAINING EXOCYCLICGROUPS SUITABLE FOR COORDINATION AND THEIRINTERACTION WITH TRANSITION METAL IONS

Acetylinic Cyclophosphazenes

Phosphino Cyclophosphazenes

Metallocenyl Cyclophosphazenes

Pyrazolyl Cyclophosphazenes

CYCLOPHOSPHAZENE LIGANDS CONTAININGOTHER TYPES OF NITROGEN DONORS

MULTI-ANIONIC CYCLOPHOSPHAZENES

CONCLUSIONS

ACKNOWLEDGEMENTS

REFERENCES

Chapter 35: PHOSPHAZENES WITH PYRIDINE GROUPS

INTRODUCTION

2. SYNTHETIC STRATEGIES

2.1 Nucleophilic Substitution of [NPX2]

2.2 Condensation

2.3 Functionalization of Organic Spacer Groups

2.4 Formation of Pyridine 1-Oxide Salts

2.5 Thermal Polymerization of Hexakis(pyridyloxy)cyclotriphosphazenes

3. PROPERTIES OF PYRIDYLALKYLAMINOFUNCTIONALIZED POLYPHOSPHAZENES

4. REACTION PROFILES

4.1 Coordination Chemistry of Pyridylalkylamino and PyridylalkoxyFunctionalized Cyclotriphosphazenes

4.2 Miscellaneous Coordination Compounds

4.3 Quarternization of Phosphazens with 4-Pyridylamino Groups

4.4 Metal Uptake and Extraction

5. CONCLUSIONS

ACKNOWLEDGEMENT

REFERENCES

Chapter 36: METAL - PHOSPHORUS 􀂱 NITROGENHETEROCYCLES, METALLACYCLOPHOSPHAZENESAND IMIDODIPHOSPHATO METAL COMPLEXES

ABSTRACT

INTRODUCTION

METALLACYCLOPHOSPHAZENES

REACTIVITY

CHARACTERIZATION

IMIDODIPHOSPHATO METAL COMPLEXES

METALLACYCLOPHOSPHAZENES AND IMIDODIPHOSPHATO METALCOMPLEXES AS PRECURSORS FOR POLYMERIC MATERIALS

SUMMARY

ACKNOWLEDGEMENT

REFERENCES

Chapter 37: POLYMER MESOPHASES AND NANOSTRUCTUREDMATERIALS BASED ON PHOSPHAZENES:THE NMR PERSPECTIVE

1. INTRODUCTION

2. POLYPHOSPHAZENES AND THE FORMATION OF THE MESOPHASES

3. SUPRAMOLECULAR ADDUCTS OF SPIROCYCLOPHOSPHAZENES

4. PERSPECTIVES: THE FORMATION OF ORGANIC ZEOLITES ANDGAS DIFFUSION INTO THE NANOPOROUS MATERIALS

ACKNOWLEDGEMENTS

REFERENCES

Chapter 38: CYCLOPHOSPHAZENES WITH P-C BOND(S)I 􀂱 SYNTHESES AND REACTIVITY

INTRODUCTION

A 􀂱 SYNTHESES

A-I- Ammonolysis of Alkyl- or Aryl-substituted Phosphorus-(V) Halides

A- II - Cyclization of Preformed Linear Precursors

A - III - Friedel-Crafts Reactions

A-IV - Carbanionic Displacement upon Halocyclophosphazenes

B 􀂱 REACTIVITY

B-I- Thermal Stability of Cyclophosphazenes

B-II 􀂱 Nucleophilic Substitutions on Cyclophosphazenes

B-III 􀂱 Electrophilic Reactions of Cyclophosphazenes

BIBLIOGRAPHY

Chapter 39: CYCLOPHOSPHAZENES WITH P-C BOND(S)II - NMR 􀂱 COMPLEXING PROPERTIES

A.- NMR

A.I.- 31P Chemical Shifts

A.II.- PNP Coupling Constants

A.III.- 13C Substituent Effects of Cyclotriphosphazenes on Aromatic Groups

A.IV.- 13C-31P Coupling Constants

B.- COMPLEXING PROPERTIES

B.I.- Introduction

B.II.- Coordination via the Phosphorus or Nitrogen Atoms of theCyclotriphosphazene Skeletal

B.III.- Coordination via Substituents of Cyclophosphazene SkeletalPhosphorus Atoms

B.IV.- Coordination via Both Skeletal Nitrogen and Substituents ofPhosphorus Atoms

ACKNOWLEDGEMENTS

REFERENCES

Chapter 40: RAMAN SPECTRA OF SHORT LINEAR AND CYCLICMOLECULAR OLIGOMERS AND OF POLYMERICCHLOROPHOSPHAZENES

EXPERIMENTAL AND COMPUTATIONAL SECTION

RAMAN SPECTRA

COMPUTATIONAL METHODS

RESULTS AND DISCUSSION

REFERENCES

ABOUT THE EDITORS

MARIO GLERIA

ROGER DE JAEGER

LIST OF CONTRIBUTORS

INDEX

Chapter

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