Phosphorus-Nitrogen Compounds - 1st Edition - ISBN: 9780120505609, 9780323147514

Phosphorus-Nitrogen Compounds

1st Edition

Cyclic, Linear, and High Polymeric Systems

Authors: H Allcock
eBook ISBN: 9780323147514
Imprint: Academic Press
Published Date: 28th January 1972
Page Count: 512
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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


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


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© Academic Press 1972
Academic Press
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H Allcock

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