Halogen Chemistry

Contributors to Volume 3

Preface

Contents of Volumes 1 and 2

Halides Containing Multicentered Metal-Metal Bonds


1. Introduction


2. Factors Influencing Metal-Metal Bond Formation


3. Compounds Based on the (M6X12)2+ Core

A. Introduction

B. Monomeric Complexes

C. Binary Halides

D. Magnetism, Spectra and Bonding


4. Compounds Based on the (M6X8)4+ Core

A. Introduction

B. Monomeric Complexes

C. Binary Halides

D. Spectra, Magnetism and Bonding


5. Compounds Based on the (Re3X3)6+ Core

A. Introduction

B. Monomeric Complexes

C. Binary Halides

D. Spectra, Magnetism and Bonding


6. Other Compounds Containing Multicentered Metal-Metal Bonding

A. Introduction

B. Halogen Bridges

C. Oxygen Bridges

D. No Bridging Atoms

References

The Nature of Metal-Halogen Bonds


1. Introduction


2. Experimental

A. Neutral Molecules

B. Complex Ions


3. Tables of Coordinate Bond Energies

A. Neutral Metal Halides

B. Metal Halide Complex Anions


4. Other Properties Related to Bonding

A. Electron Spin Resonance

B. Nuclear Magnetic Resonance Chemical Shifts

C. Nuclear Quadrupole Resonance

D. Decrease in Spin-Orbit Coupling Constants

E. Decrease in Inter-electronic Repulsion Integrals: The Nephelauxetic Effect

F. Dipole Moments

G. Force Constants

H. X-Ray Diffraction


5. Theoretical

A. The Hard Sphere Ion Model

B. Polarizable Ion Model

C. Localized Molecular Orbital Method

D. Modified Wolfsberg-Helmholz Method

References

Review of Metal-Halogen Vibrational Frequencies


1. Introduction


2. Metal-Fluorine Vibrational Frequencies

A. Octahedral Molecules

B. Tetrahedral Molecules

C. Heptafluorides

D. Other Stereochemistries

E. Assignments in Metal Complexes


3. Metal-Chlorine, Metal-Bromine, and Metal-Iodine Vibrational Frequencies

A. Octahedral Hexahaloanions

B. Tetrahedral Anions

C. Square Planar Ions

D. Five-Coordinate Halides

E. Linear Species

F. Assignments in Metal Complexes


4. Conclusion

References

The Halides of Niobium and Tantalum


1. Fluorine Compounds

A. Pentafluorides

B. Sub-Fluorides


2. Chlorine Compounds

A. Pentachlorides

B. Sub-Chlorides


3. Bromine Compounds

A. Pentabromides

B. Sub-Bromides


4. Iodine Compounds

A. Pentaiodides

B. Sub-Iodides

References

Pentahalides of the Transition Metals


1. Introduction


2. Pentahalides

A. Physical Properties and Structure

B. Preparation of the Pentahalides

C. Chemical Properties


3. Mixed Pentahalides

References

Halide Chemistry of Chromium, Molybdenum and Tungsten


1. General Introduction


2. Chromium

A. Chromium(I) (d5)

B. Chromium(II) (d4)

C. Chromium(III) (d3)

D. Chromium(IV) (d2)

E. Chromium(V) (d1)

F. Chromium{VI) (d0)


3. Molybdenum and Tungsten

A. Molybdenum and Tungsten (0,I)(d6,d5)

B. Molybdenum and Tungsten (II)(d4)

C. Molybdenum and Tungsten (III)(d3)

D. Molybdenum and Tungsten (IV)(d2)

E. Molybdenum and Tungsten(V)(d1)

F. Molybdenum and Tungsten(VI)(d0)

Recent Developments

References

The Halogen Chemistry of the Actinides


1. Introduction


2. The Trivalent Actinides

A. General Chemistry

B. Trifluorides

C. Trichlorides

D. Tribromides

E. Tri-Iodides

F. Mixed Halides

G. Oxyhalides


3. The Tetravalent Actinides

A. General Chemistry

B. Tetrafluorides

C. Tetrachlorides

D. Tetrabromides

E. Tetraiodides

F. Mixed Halides

G. Halo Complexes

H. Oxyhalides


4. The Pentavalent Actinides

A. General Chemistry

B. Pentafluorides

C. Intermediate Fluorides

D. Pentachlorides

E. Pentabromides

F. Pentaiodides

G. Mixed halides

H. Halo Complexes

J. Oxyhalides


5. The Hexavalent Actinides

A. General Chemistry

B. Hexafluorides

C. Uranium Hexachloride

D. Oxyhalides

References

Halogeno Metal Carbonyls and Related Compounds


1. Introduction


2. Methods of Preparation

A. Copper Subgroup

B. Nickel Subgroup

C. Cobalt Subgroup

D. Iron Subgroup

E. Manganese Subgroup

F. Chromium Subgroup


3. Chemical and Physical Properties


4. Structures of Halogeno Metal Carbonyls

A. X-Ray Determinations

B. Structure Investigations by Physical Methods


5. Reactions of Halogeno Metal Carbonyls

A. Mononuclear Compounds

B. Polynuclear Compounds

C. Anionic Compounds


6. Mechanistic Studies


7. Stability of Halogeno Metal Carbonyls

References

Author Index

Subject Index