Phosphorus-Nitrogen Compounds

Phosphorus-Nitrogen Compounds

Cyclic, Linear, and High Polymeric Systems

1st Edition - January 28, 1972

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  • Author: H Allcock
  • eBook ISBN: 9780323147514

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Phosphorus-Nitrogen Compounds: Cyclic, Linear, and High Polymeric Systems concerns itself with the chemistry of compounds containing alternating phosphorus - nitrogen atoms in the skeleton. The monograph aims to be an introduction to phosphorus-nitrogen chemistry, a review of advances in the field, and reference work. The text is divided into three parts. Part I covers the introduction, historical background, and nomenclature of phosphorus-nitrogen compounds and the theories in bonding and structure of phosphazenes and phosphazanes. Part II deals with reactions such as the synthesis of the phosphorus-nitrogen skeleton, hydrolysis of phosphazenes and phosphazanes, and the aminolysis of halophosphazenes. Part III discusses polymer chemistry and includes topics such as polymerization, depolymerization, and phosphazene polymers. The book is recommended for students and practitioners in the field of chemistry, especially those concerned with phosphorus nitrogen compounds and polymeric systems.

Table of Contents

  • Preface

    Part I Introduction and Structural Chemistry

    Chapter 1. Introduction, Historical Background, and Nomenclature

    A. Introduction

    B. Historical Background

    C. Nomenclature


    Chapter 2. Theories of Bonding in Phosphazenes

    A. Introduction

    B. Anomalies of the Phosphorus-Nitrogen Bond

    C. Bonding Characteristics of Nitrogen

    D. Bonding Characteristics of Phosphorus

    E. The Zwitterionic Phosphazene Model

    F. The Phosphorus 4s or 4p Model

    G. The dπ-pπ Model

    H. Comparisons with pπ-pπ Aromatic Systems


    Chapter 3. The Structure of Phosphazenes and Phosphazanes

    A. Introduction

    B. X-Ray Diffraction Data

    C. Thermochemical Bond Strengths and π-Bond Energy

    D. Vibrational Spectra

    Ε. Ultraviolet Spectra

    F. Polarography

    G. Electron Spin Resonance Spectra

    H. Electrical Conductance Experiments

    I. Mass Spectrometry

    J. Dipole Moments

    K. Diamagnetic Anisotropy

    L. Basicity Measurements

    M. Nuclear Quadrupole Resonance

    N. Nuclear Magnetic Resonance

    O. Conclusions


    Part II Synthesis and Reactions

    Chapter 4. Synthesis of the Phosphorus-Nitrogen Skeleton

    A. General Survey of Synthetic Routes

    B. The Reaction between Halophosphoranes and Ammonium Halides


    Chapter 5. Hydrolysis of Phosphazenes and Phosphazanes

    A. General Features

    B. Hydrolysis of Halophosphazenes

    C. Hydrolysis of Cyclophosphazanes

    D. Hydrolysis of Organophosphazenes and Organophosphazanes


    Chapter 6. Reactions of Halophosphazenes with Alkoxides, Aryloxides, and Thiolates

    A. Introduction

    B. Experimental Considerations

    C. Scope of the Reaction

    D. General Properties of Alkoxy-, Aryloxy-, Alkylthio-, and Arylthiophosphazenes

    E. Influence of the Nucleophile on Substitution

    F. Influence of the Halogen in Halophosphazenes

    G. Influence of Phosphazene Ring or Chain Size

    Η. Effect of the Solvent

    I. Influence of the Base

    J. Influence of Temperature

    K. Monophosphazenes and Related Compounds

    L. The Reaction Mechanism


    Chapter 7. Aminolysis of Halophosphazenes

    A. Introduction

    B. Experimental Considerations

    C. Scope of the Aminolysis Reaction

    D. General Properties and Uses of Aminophosphazenes

    E. Influence of the Amine on Substitution

    F. Influence of Other Substituents on the Aminolysis Reaction

    G. Cis-Trans Isomerization during Substitution

    H. Influence of Halogen Bound to Phosphorus

    I. Influence of Phosphazene Ring or Chain Size

    J. Monophosphazenes and Cyclophosphazanes

    K. Effect of Solvent and Temperature on Aminolysis

    L. Influence of the Hydrohalide Acceptor

    M. The Reaction Mechanism


    Chapter 8. Metathetical Reactions

    A. Introduction

    B. Exchange of Chlorine by Chlorine

    C. Replacement of Chlorine by Fluorine

    D. Replacement of Bromine by Fluorine and Chlorine

    E. Replacement of Chloro by Cyano Groups

    F. Replacement of Chloro by Isothiocyano Groups

    G. Replacement of Chloro by Azido Groups

    H. Exchange between Organic Ligands


    Chapter 9. Reactions of Phosphazenes with Organometallic Reagents

    A. Introduction

    B. Interaction of Halophosphazenes with Organolithium Reagents

    C. The Reactions of Halophosphazenes with Grignard Reagents

    D. Reactions of Organophosphazenes with Organometallic Reagents


    Chapter 10. Friedel-Crafts Substitutions

    A. Scope and Reaction Characteristics

    B. The Mechanisms of Friedel-Crafts Arylation


    Chapter 11. Complex and Adduct Formation

    A. Introduction

    B. Complexes between Phosphazenes and Inorganic Halides or Organometallic Compounds

    C. "Onium"-Type Complexes

    D. π and Charge-Transfer Complexes

    E. Crystalline Inclusion Clathrates


    Chapter 12. Phosphazenes as BrØnsted-Lowry Bases

    A. Introduction

    B. Preparation of Hydrohalide Adducts

    C. Structure of the Adducts

    D. Degree of Protonation

    Ε. pKa Measurements of Phosphazenes in Nitrobenzene and Water

    F. Influence of Different Substituents

    G. Theoretical Implications of Basicity Studies


    Chapter 13. Rearrangements

    A. Introduction

    B. Alkoxyphosphazene-Oxophosphazane Rearrangements

    C. Cis-Trans Isomerizations


    Chapter 14. Skeletal Bond Cleavage, Thermolysis, and Other Reactions

    A. Skeletal Bond Cleavage Reactions

    B. Thermolysis Reactions

    C. Other Reactions


    Part III Polymer Chemistry

    Chapter 15. Polymerization and Depolymerization

    A. Introduction

    B. Theories of Ring-Polymer Equilibria

    C. General Features of Hexachlorocyclotriphosphazene Polymerization

    D. Effect of Different Ligands

    E. The Polymerization-Depolymerization Mechanism


    Chapter 16. Phosphazene Polymers

    A. Types of Phosphazene Polymers

    B. Physical Characteristics of Different Polymers

    C. Linear Poly(dihalophosphazenes)

    D. Linear Organophosphazene Polymers

    E. Cyclolinear Polymers

    F. Cyclomatrix Polymers


    Appendix I. Bond Angles and Interatomic Distances for Phosphorus-Nitrogen Compounds

    Tabulated Material


    Appendix II. Characterization Data for Phosphazenes and Phosphazanes

    Tabulated Material


    Author Index

    Subject Index

Product details

  • No. of pages: 512
  • Language: English
  • Copyright: © Academic Press 1972
  • Published: January 28, 1972
  • Imprint: Academic Press
  • eBook ISBN: 9780323147514

About the Author

H Allcock

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