The Chemistry of Ruthenium - 1st Edition - ISBN: 9780444423757, 9781483289908

The Chemistry of Ruthenium, Volume 19

1st Edition

Editors: R. J. H. Clark
Authors: E.A. Seddon K.R. Seddon
eBook ISBN: 9781483289908
Imprint: Elsevier Science
Published Date: 1st July 1984
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Table of Contents


Frontispiece

Abbreviations

Sign Conventions and Conversion Factors

Chapter 1 Introduction

1.1 Scope and Vera Causa

1.2 Ordering of the Chapters

1.3 Ordering within the Chapters

1.4 Discovery and Early History of Ruthenium

1.5 Extraction and Purification of Ruthenium

1.6 Analysis

1.7 Applications and Uses of Ruthenium

1.8 Isotopes of Ruthenium

1.9 Physical Properties of Ruthenium

1.10 Chemical Properties of Ruthenium

Chapter 2 Oxidation State

2.1 What is Oxidation State?

2.2 Does Oxidation State have a Chemical Significance?

2.3 The MLX System

2.3.1 Definitions and Scope

2.3.2 The Classification of Neutral Molecules Containing Monodentate Ligands

2.3.3 The Rules for Classifying Vovalent Anions and Cations

2.3.4 Polyfunctional Atoms and Polydentate Ligands

2.3.5 Bridging Ligands

2.4 MLX Plots

2.4.1 Construction of MLX Plots

2.4.2 Use of MLX Plots

2.5 Mössbauer Spectroscopy

Chapter 3 Ruthenium(VIII)

3.1 Ruthenium(VIII) Fluoride

3.2 Ruthenium(VIII) Oxide

3.2.1 Physical and Spectroscopic Properties

3.2.2 Preparation

3.2.3 Adducts

3.2.4 Reactions

3.2.5 Oxidation of Organic Compounds

Addenda

Chapter 4 Ruthenium(VII)

4.1 Potassium Ruthenate(VII)

4.1.1 Preparation

4.1.2 Physical and Spectroscopic Properties

4.1.3 Reactions

4.2 Sodium Ruthenate(VII)

4.3 μ-Oxo-Bis[Trioxo(1,10-Phenanthroline)Ruthenium(VII)]

Chapter 5 Ruthenium(VI)

5.1 Ruthenium(VI) Fluoride

5.2 Ruthenium(VI) Oxide Tetrafluoride

5.3 Potassium Octafluororuthenate(VI)

5.4 Dioxoruthenium(VI) Complexes

5.4.1 Tetrahalodioxoruthenates(VI) and Related Species

5.4.2 Bis(Amine)Dichlorodioxoruthenium(VI), Bis(Amine)Dihydroxodioxoruthenium(VI) and Related Species

5.5 Nitridoruthenium(VI) Complexes

5.5.1 Tetra- and Penta-Halonitridoruthenates(VI)

5.5.2 Trichloronitridoruthenium(VI) Adducts

5.6 Ruthenium(VI) Oxide

5.7 Metal Ruthenates(VI)

5.7.1 Preparation

5.7.2 Physical and Spectroscopic Properties

5.7.3 Reactions

5.8 Ruthenium(VI) Sulphates and Related Species

5.9 Ruthenium(VI) Amides

5.9.1 Ruthenium(VI)-1,2-Diaminoethane Complex

5.9.2 Ruthenium(VI)-Ammonia Derivative

Addenda

Chapter 6 Ruthenium(V)

6.1 Ruthenium(V) Fluoride

6.2 Metal Hexafluororuthenates(V)

6.3 Non-Metal Hexafluororuthenates

6.3.1 Xenon Salts

6.3.2 Dioxygenyl Hexafluororuthenate(V)

6.3.3 Other Hexafluororuthenates(V)

6.4 Bis(Tricarbonyldifluororuthenium(II)-Ruthenium(V) Fluoride)

6.5 Caesium Tetracyanobis(Isocyanato)Oxoruthenate(V)

6.6 Ruthenium(V) Oxide

6.7 Quaternary Ruthenium(V) Oxides

6.8 Sodium and Lithium Ruthenates(V)

Addenda

Chapter 7 Ruthenium(IV)

7.1 Ruthenium(IV) Halides and Oxohalides

7.1.1 Ruthenium(IV) Fluoride

7.1.2 Ruthenium(IV) Chloride

7.1.3 Ruthenium(IV) Bromide and Ruthenium(IV) Iodide

7.1.4 Ruthenium(IV) Oxohalides and Related Species

7.2 Hexahaloruthenates(IV)

7.2.1 Hexafluororuthenates(IV)

7.2.2 Hexachlororuthenates(IV)

7.2.3 Hexabromoruthenates(IV)

7.2.4 Hexaiodoruthenates(IV)

7.3 μ-Oxo-Bis[Pentahaloruthenates(IV)] and Related Complexes

7.3.1 Potassium μ-Oxo-Bis[Pentachlororuthenate(IV)] Monohydrate

7.3.2 Potassium μ-Oxo-Bis[pentabromoruthenate(IV)]

7.4 μ-Nitrido-Bis[Aquatetrahaloruthenates(IV)] and Related Complexes

7.5 Adducts of Ruthenium(IV) Halides and Related Complexes

7.5.1 Complexes with Nitrogen-Donor Ligands

7.5.2 Phosphineiminato Complexes

7.5.3 Triphenylphosphine-Carbon Disulphide Complex

7.5.4 Phthalocyanine-Tetrasulphonate Complexes

7.5.5 Selenourea Complexes

7.5.6 o-Diolato Complexes

7.6 Aqueous Chemistry and Halo-Aqua Complexes of Ruthenium(IV)

7.7 Ruthenium(IV) Oxide

7.8 Metal Ruthenates(IV)

7.8.1 Metal Ruthenium Trioxides, MRu03, and Related Structures

7.8.2 Pyrochlores, M2RU2O7, and Defect Pyrochlores, M2RU2O6

7.8.3 Sr2RuO4

7.8.4 Other Ternary Ruthenium(IV) Oxides

7.8.5 Other Ruthenium(IV) Oxide Derivatives

7.9 Ruthenium(IV) Chalcogenides

7.10 Ruthenium(IV) Nitrates, Sulphates, Carboxylates and Related Species

7.10.1 Ruthenium(IV) Nitrates

7.10.2 Ruthenium(IV) Sulphates

7.10.3 Ruthenium(IV) Oxalates

7.10.4 Ruthenium(IV) Citrates

7.10.5 Ruthenium(IV) Edta Complexes

7.10.6 Ruthenium(IV) β-Diketonates

7.10.7 Ruthenium(IV) Dithiocarbamates

7.11 Ruthenium(IV) Hydrides

7.11.1 Tetrahydridotris(Triphenylphosphine)Ruthenium(IV)

7.11.2 Trihydridobis[Bis(Diphenylphosphino)Propane]Ruthenium(IV) Hexafluorophosphate and Related Complexes

7.11.3 Ruthenium(IV) Carbaborane Complexes

7.11.4 Ruthenium(IV) Silyl Complexes

7.12 Ruthenium(IV) Allyl Complexes

7.12.1 Dichloro(Ddodeca-2,6,10-Triene-1,12-Diyl)Ruthenium(IV)

7.12.2 Dichloro-Di-μ-Chloro-Bis(2,7-Dimethyl-Octa-2,6-Diene-1,8-Diyl)Diruthenium(IV)

7.13 Ruthenium(IV) Cyclopentadienyl Complexes

7.14 Mixed Oxidation State (IV/III) Complexes

7.14.1 Ruthenium Red and Related Complexes

7.14.2 μ-Oxo-Bis[Chlorobis(2,2'-Bipyridine)Ruthenium(IV/III)] Hexafluorophosphate

Addenda

Chapter 8 Ruthenium(III)

8.1 Ruthenium(III) halides

8.1.1 Ruthenium(III) Fluoride

8.1.2 Ruthenium(III) Chloride

8.1.3 Ruthenium(III) Bromide

8.1.4 Ruthenium(III) Iodide

8.2 Hexahaloruthenates(III) and Related Complexes

8.2.1 Hexafluororuthenates(III)

8.2.2 Hexachlororuthenates(III) and Related Species

8.2.3 Hexabromoruthenates(III) and Related Spcies

8.3 Ruthenium(III) Halo-Aqua Systems

8.3.1 Aquapentahaloruthenates(III)

8.3.2 Diaquatetrahaloruthenates(III)

8.3.3 Triaquatrihaloruthenium(III)

8.3.4 Tetraaquadihaloruthenium(III) Complexes

8.3.5 Pentaaquahaloruthenium(III) Complexes

8.3.6 Catalytic Activity of Ruthenium(III) Aquachloro Systems

8.4 Hexaaquaruthenium(III)

8.5 Ruthenium(III) Oxide and Metal Ruthenates(III)

8.6 Ruthenium(III) Carboxylates

8.6.1 Catena-μ-Chlorotetra-μ-Carboxylato-(0,0')-Diruthenium(III,II)

8.6.2 Hexa-μ-Carboxylato-(O,O')-μ3-Oxo-Triruthenium(III) Salts and Related Complexes

8.6.3 Ruthenium(III)-Edta Complexes and Related Species

8.6.4 Ruthenium(III) Oxalate Complexes

8.6.5 Ruthenium(III) Citrates and Related Species

8.6.6 Other Complexes

8.7 Nitro, Nitrato and Sulphato Complexes of Ruthenium(III)

8.8 β-Diketonate Complexes of Ruthenium(III) and Related Complexes

8.8.1 Tris(2,4-Pentanedionato)Ruthenium(III)

8.8.2 Other β-Diketonate Complexes

8.8.3 Tropolonato Complexes

8.8.4 Diolato Complexes

8.9 Ruthenium(III) Complexes with Oxygen-Donor Ligands

8.10 Ruthenium(III) Complexes with Sulphur-Donor Ligands

8.11 Thio and Dithio-β-Diketonate Complexes of Ruthenium(III) and Related Complexes

8.11.1 Monothio Derivatives

8.11.2 Dithio Derivatives

8.11.3 Dithiobenzil Complexes

8.12 Ruthenium Dithiocarboxylates and Related Complexes

8.12.1 Ruthenium(III) Dithiocarboxylate Complexes

8.12.2 Ruthenium(III) Dithiophosphinates

8.12.3 Ruthenium(III) Dithiolate Complexes

8.13 Tris(Dithiocarbamato)Ruthenium(III) and Related Complexes

8.14 Hexaamineruthenium(III) Salts

8.15 Halopentaammineruthenium(III) Salts and Related Complexes

8.15.1 Chloropentaammineruthenium(III) Salts

8.15.2 Bromo- and Iodo-Pentaammineruthenium(III) Salts

8.15.3 Pseudohalopentaammineruthenium(III) Salts

8.15.4 Hydroxopentaammineruthenium(III) Salts

8.15.5 Carboxylatopentaammineruthenium(III) Salts

8.15.6 Other Acidopentaammineruthenium(III) Salts

8.16 Dihalotetraammineruthenium(III) Salts and Related Complexes

8.16.1 Dihalotetraammineruthenium(III) Salts

8.16.2 Related Complexes

8.17 Trihalotriammineruthenium(III) Complexes and Related Compounds

8.18 [(NH3)5RuL]3+ and [(NH3)4RuL2]3+ Salts and Related Species

8.18.1 Aquaammineruthenium(III) Salts

8.18.2 Complexes with Sulphur-Donor Ligands

8.18.3 Complexes with Organonitriles

8.18.4 Complexes with Other Amines

8.18.5 Complexes with Purines and Related Ligands

8.19 1,2-Diaminoethane Complexes of Ruthenium(III) and Related Species

8.19.1 Tris(1,2-Diaminoethane)Ruthenium(III) Salts

8.19.2 Bis(1,2-Diaminoethane)Ruthenium(III) Salts and Related Species

8.19.3 Azide Complexes

8.20 Other Amine Complexes of Ruthenium(III)

8.20.1 Tris(Amine)Trihaloruthenium(III)

8.20.2 Anionic and Cationic Complexes

8.20.3 Hydrazine Complexes

8.20.4 Bifunctional Amine Complexes

8.20.5 Phthalocyanine and Porphyrin Complexes

8.20.6 Other Complexes

8.21 2,2'-Bipyridine and 1,10-Phenanthroline Complexes of Ruthenium(III)

8.21.1 Tris(2,2'-Bipyridine)Ruthenium(III) Complexes and Related Species

8.21.2 Bis(2,2,-Bipyridine)Ruthenium(III) Complexes and Related Species

8.21.3 Mono(2,2'-Bipyridine)Ruthenium(III) Complexes and Related Species

8.21.4 Oxo-Bridged Dimers

8.22 Phosphine and Arsine Complexes of Ruthenium(III)

8.22.1 Simple Adducts

8.22.2 Mixed Adducts

8.22.3 Anionic and Cationic Complexes

8.23 Ruthenium(III) Cyanides, Thiocyanates and Azides

8.23.1 Ruthenium(III) Cyanides

8.23.2 Ruthenium(III) Thiocyanates

8.23.3 Ruthenium(III) Azides

8.24 Ruthenium(III) Carbonyl Complexes

8.24.1 Monomeric Halocarbonyl Complexes

8.24.2 Dimeric Carbonyl Complexes

8.25 Ruthenium(III) Organometallic Chemistry

8.26 Catalytic Activation of Molecular Hydrogen by Ruthenium(III)

8.27 Mixed Oxidation State (III/II) Complexes

8.27.1 Tri-μ-Chloro-Bis[Chlorobis(Tributylphosphine)Ruthenium(III/II)] and Related Species

8.27.2 Pentakis(Dimethyldithiocarbamato)Diruthenium(III/II)

8.27.3 Tri-μ-Chloro-Bis[Triammineruthenium(III/II)] Chloride and Related Complexes

8.27.4 μ-Pyrazine-Bis[Pentaammineruthenium(III/II)] Salts and Related Complexes

Addenda

Chapter 9 Ruthenium(II)

9.1 Ruthenium(II) Halides

9.1.1 Ruthenium(II) Fluoride

9.1.2 Ruthenium(II) Chloride

9.1.3 Ruthenium(II) Bromide

9.1.4 Ruthenium(II) Iodide

9.2 Ruthenium(II) Halide Complexes

9.2.1 Blue Ruthenium(II) Solutions: Ruthenium(II) Chloride Complexes

9.2.2 Violet-Blue Ruthenium(II) Solutions: Ruthenium(II) Bromide Complexes

9.2.3 Ruthenium(II) Iodide Complexes

9.2.4 Monomeric Aquachlororuthenium(II) Complexes

9.3 Hexaaquaruthenium(II)

9.4 Ruthenium(II) Oxide

9.5 β-Diketonate Complexes of Ruthenium(II)

9.6 Sulphoxide Complexes of Ruthenium(II)

9.6.1 Dimethylsulphoxide Complexes

9.6.2 Other Complexes

9.7 Ruthenium(II) Complexes with Sulphide Ligands

9.8 Dithiocarbamate Complexes of Ruthenium(II)

9.9 Dithiolene, Thiol and Thione Complexes of Ruthenium(II)

9.9.1 Dithiolene Complexes

9.9.2 Thiol and Thione Complexes

9.10 Hexaammineruthenium(II) Salts

9.11 Halopentaammineruthenium(II) Salts and Related Species

9.12 Dihalotetraammineruthenium(II) Salts

9.13 [Ru(NH3)5L]2+ and [Ru(NH3)4L2]2+ Salts and Related Species

9.13.1 Aquaammineruthenium(II) Salts

9.13.2 Adducts with Oxovanadium(IV) Complexes

9.13.3 Complexes with Sulphur-Donor Ligands

9.13.4 Dimethylsulphoxide Complexes

9.13.5 Sulphur Dioxide Complexes, and Related Sulphito and Hydrogensulphito Species

9.13.6 Complexes with Pyridine and Related Ligands

9.13.7 Complexes with Pyrazine and Related Ligands

9.13.8 Complexes with 4,4'-Bipyridine and Related Ligands

9.13.9 Complexes with Purines and Related Ligands

9.13.10 Nitrile Complexes

9.13.11 Dinitrogen Oxide Complexes

9.13.12 Complexes with Phosphite Ligands

9.13.13 Carbonyl Complexes

9.13.14 Alkene and Alkyne Complexes

9.14 1,2-Diaminoethane Complexes of Ruthenium(II) and Related Species

9.15 Ruthenium(II) Complexes with Other N-Donor Ligands

9.15.1 Pyridine Complexes

9.15.2 Primary Amine Complexes

9.15.3 Nitrile Complexes

9.15.4 Ruthenium(II)-Edta Complexes

9.15.5 Miscellaneous

9.16 Dinitrogen Complexes of Ruthenium(II)

9.16.1 Pentaammine(Dinitrogen)Ruthenium(II) Salts and Related Species

9.16.2 μ-Dinitrogen-Bis[Pentaammineruthenium(II)] Salts and Related Species

9.16.3 μ-Dinitrogen-Bis[Pentaaquaruthenium(II)] Tetrafluoroborate

9.16.4 1,2-Diaminoethane Ruthenium(II) Complexes

9.16.5 Bis(Dinitrogen) Complexes

9.16.6 Tetrahydrofuran Ruthenium(II) Complexes of Dinitrogen

9.16.7 Phosphine Ruthenium(II) Complexes of Dinitrogen

9.16.8 Arsine Ruthenium(II) Complexes of Dinitrogen

9.17 2,2'-Bipyridine and 1,10-Phenanthroline Complexes of Ruthenium(II)

9.17.1 Tris(2,2'-Bipyridine)Ruthenium(II) Complexes and Related Species

9.17.2 Mixed-Ligand Complexes

9.17.3 Bis(2,2'-Bipyridine)Ruthenium(II) Complexes and Related Species

9.17.4 Mono(2,2,-Bipyridine)Ruthenium(II) Complexes and Related Species

9.18 Ruthenium(II) Phthalocyanine and Porphyrin Complexes

9.18.1 Phthalocyanine Complexes

9.18.2 Porphyrin Complexes

9.19 Haloruthenium(II) Phosphine and Arsine Complexes

9.19.1 Complexes with Simple Monodentate and Bidentate Ligands

9.19.2 Complexes with Polydentate Ligands

9.19.3 Complexes with Chiral Phosphines

9.19.4 Complexes with Ambidentate Ligands

9.19.5 Mixed Ligand Complexes

9.20 Hydridoruthenium(II) Phosphine and Arsine Complexes

9.20.1 Neutral Dihydrido Complexes

9.20.2 Tetrahydroborate Derivatives

9.20.3 Neutral Monohydride Complexes

9.20.4 Cationic Hydrido Complexes

9.20.5 Cationic Hydridocarbonyl Complexes

9.21 Ruthenium(II) Phosphine and Arsine Complexes with Other Secondary Ligands

9.21.1 Methanoate Complexes

9.21.2 Carboxylate Complexes

9.21.3 Monoalkylcarbonate and Carbamate Complexes

9.21.4 Ketone and β-Diketonate Complexes

9.21.5 Nitrate, Sulphate, Carbonate, Organic Arsonate, Hydroxide and Alkoxide Complexes

9.21.6 Dithiomethanoate and Thiomethanoate Complexes

9.21.7 Thiocarboxylate Complexes

9.21.8 Dithiocarbamate, Thiocarbamate, Dithiocarbonate and Thiocarbonate Complexes

9.21.9 Phosphinodithioate Complexes

9.21.10 Dithiocarbonimidate Complexes

9.21.11 Dithiolene Complexes

9.21.12 Formimidoyl, Iminoacyl and Isocyanate Complexes

9.21.13 Thioformamido Complexes

9.21.14 Formamidinato Complexes

9.21.15 Triazenide Complexes

9.21.16 Amido and Ureylene Complexes

9.21.17 Schiff Base Complexes

9.21.18 CS, CS2 and CS2Me Complexes, and Related Species

9.21.19 SO2 Complexes and their Derivatives

9.21.20 Ethene and Dioxygen Complexes

9.22 Halocarbonylruthenium(II) Complexes

9.22.1 Tetrakis{Tricarbonyldifluororuthenium(II)}

9.22.2 Chloro-, Bromo- and Iodo-Carbonylruthenium(II) Complexes

9.22.3 Pseudohalocarbonylruthenium(II) Complexes

9.22.4 Complexes with Neutral Ligands

9.22.5 Complexes with CS

9.23 Hydridocarbonylruthenium(II) Complexes

9.23.1 Tetracarbonylbis(Hydrido)Ruthenium(II)

9.23.2 Complexes with Neutral Ligands

9.24 Ruthenium(II) Cyanides

9.24.1 Hexacyanoruthenates(II) and 'Binary' Cyanides

9.24.2 Pentacyanonitroruthenates(II)

9.24.3 Binuclear Complexes

9.25 Isonitrile Complexes of Ruthenium(II)

9.25.1 Hexakis- and Pentakis- (Isonitrile)Ruthenium(II)

9.25.2 Tetrakis(Isonitrile)Ruthenium(II) Complexes

9.25.3 Bis(Isonitrile)Ruthenium(II) Complexes

9.25.4 Mono(Isonitrile)Ruthenium(II) Complexes

9.25.5 Dimeric Complexes

9.26 Carbene Complexes

9.27 Cycloruthenated Complexes

9.27.1 Alkylphosphine Derivatives

9.27.2 Triphenylphosphine Derivatives

9.27.3 Arylphosphite Derivatives

9.27.4 Complexes Derived from N-Donor Ligands

9.27.5 Carbene Derivatives

9.28 Alkyl-, Acyl- and Aryl- Ruthenium(II) Phosphine and Arsine Complexes

9.28.1 Halo, Hydrido, Dialkyl or Diaryl Derivatives

9.28.2 Carbonyl Derivatives

9.28.3 Acyl Derivatives

9.28.4 Carbamoyl Derivatives

9.29 Fluoroalkene Complexes and Related Species

9.30 Allyl Complexes

9.30.1 Carbonyl Derivatives

9.30.2 Phosphine and Phosphite Derivatives

9.30.3 Diene Derivatives

9.30.4 Azepine Derivatives

9.31 Diene Complexes

9.31.1 Polymeric Complexes

9.31.2 Dimeric Complexes

9.31.3 Simple adducts

9.31.4 Bis(Chelate)(Diene)Ruthenium(II) Complexes

9.31.5 Anionic Complexes

9.31.6 Cationic Complexes

9.31.7 Hydrazine-Bridged Complexes

9.32 Bis(η5-Cyclopentadienyl)Ruthenium(II) (Ruthenocene) and its Derivatives

9.32.1 Ruthenocene

9.32.2 Ruthenocene Derivatives

9.32.3 Bis(η5-Indenyl)Ruthenium(II) and Related Species

9.32.4 Optically Active Ruthenocenes, and Related Fused-Ring Systems

9.32.5 Ruthenocene Derivatives Containing Ru-Hg or Ru-Sn Bonds

9.32.6 Radioactive Labelled Ruthenocenes

9.33 Mono(η5-Cyclopentadienyl)Ruthenium(II) Derivatives

9.33.1 Monopositive Cationic Derivatives

9.33.2 Neutral Dicarbonyl Derivatives

9.33.3 Neutral Monocarbonyl Derivatives

9.33.4 Neutral Bis(Phosphine) and Bis(Arsine) Derivatives and Related Complexes

9.33.5 Dimeric Complexes

9.34 Cyclohexadienyl Complexes

9.35 Bis(Arene)Ruthenium(II) Salts and Related Species

9.35.1 Symmetrical Bis(Arene)Ruthenium(II) Salts

9.35.2 Unsymmetrical Bis(Arene)Ruthenium(II) Salts

9.35.3 (Arene)(Carbocycle)Ruthenium(II) and (Arene)(Heterocycle)Ruthenium(II) Salts

9.36 Monomeric Mono(Arene)Ruthenium(II) Complexes

9.36.1 Dipositive Cationic Salts

9.36.2 Monopositive Cationic Complexes

9.36.3 Neutral Complexes

9.36.4 Anionic Complexes

9.36.5 Carbonyl Complexes

9.36.6 Complexes with Group IVB Donor Ligands

9.36.7 Ethene Complexes

9.36.8 Poly(1-Pyrazolyl)Borato Complexes

9.36.9 Phosphinodithioate Complexes

9.36.10 Chiral Complexes

9.37 Oligomeric (Arene)Ruthenium(II) Complexes

9.37.1 Complexes of Stoicheiometry [Ru2(Arene)2X4]

9.37.2 Complexes of Stoicheiometry [Ru2(Arene)2X3]Y

9.37.3 Complexes of Stoicheiometry [Ru4+(Arene)4X4]Y4

9.38 Cycloheptadienyl, Cycloheptatrienyl and Cycloheptatriene Complexes

9.38.1 Bis(η5-Cycloheptadienyl)Ruthenium(II) and Related Complexes

9.38.2 The Tricarbonyl(η5-Cycloheptadienyl)Ruthenium(II) Cation, and Related Complexes

9.38.3 Dicarbonyl- and Monocarbonyl-(η5-Cycloheptadienyl)Ruthenium(II) Derivatives

9.38.4 Dimeric Complexes

9.38.5 Cycloheptatriene Complexes

9.39 Cyclooctadienyl, Cyclooctatrienyl, Cyclooctatetraene and Pentalene Complexes

9.39.1 Monomeric Species

9.39.2 Dimeric Species

9.39.3 Pentalene Derivatives, and Related Complexes

9.40 Complexes with Group IVB Donor Ligands

9.40.1 Trichlorostannio Complexes and Related Species

9.40.2 Trichlorosilyl and Trichlorogermyl Complexes

9.40.3 Trialkyl Silyl, Germyl and Stannyl Complexes

9.40.4 Complexes of Bidentate Silyl Ligands

9.40.5 Silylruthenium(II) Hydrides and Hydrosilylation Reactions

9.41 Carbaborane Complexes of Ruthenium(II)

9.42 Complexes with Group IIB Donor Ligands

9.43 Ruthenium(II) Hydrides

9.44 Mixed Oxidation State (II/0) Complexes

Addenda

Chapter 10 Ruthenium(I)

10.1 Ruthenium(I) Halides

10.2 Ruthenium(I) Bipyridine Complexes

10.3 Ruthenium(I) Phosphine and Arsine Complexes

10.4 Ruthenium(I) Cyanides

10.5 Ruthenium(I) Carbonyl Halides

10.6 Ruthenium(I) Carbonyl Carboxylates

10.7 Ruthenium(I) Carbonyl Complexes with Chalcogenide Ligands

10.8 Ruthenium(I) Carbonyl Phosphine Complexes

10.9 Ruthenium(I) Silyl, Germyl and Stannyl Complexes

10.10 Ruthenium(I) Carbonyl Hydrides

10.11 Acyclic Alkene Complexes

10.12 Allyl Complexes

10.13 Cyclopentadienyl Complexes

10.13.1 Carbonyl Derivatives

10.13.2 Thiocarbonyl Derivatives

10.14 Cycloheptatrienyl Complexes

10.15 Cyclooctatetraene and Cyclooctatriene Derivatives

10.16 Bicyclo Derivatives

Addenda

Chapter 11 Ruthenium(O)

11.1 Ruthenium(O) carbonyls

11.1.1 Pentacarbonylruthenium(O)

11.1.2 Nonacarbonyldiruthenium(O)

11.2 Ruthenium(O) Phosphine Complexes

11.2.1 Pentakis(Trifluorophosphine)Ruthenium(O) and Related Species

11.2.2 Pentakis(Trimethylphosphite)Ruthenium(O)

11.2.3 Di{l,2-Bis(DimethyIphosphino)Ethane}Ruthenium(O)

11.2.4 [HRu(PF3)4]-

11.3 Ruthenium(O) Carbonyl Phosphine Complexes

11.3.1 Mono(Phosphine)Tetracarbonylruthenium(O)

11.3.2 Bis(Phosphine)Tricarbonylruthenium(O) and Related Arsine Complexes

11.3.3 Tris(Phosphine)Dicarbonylruthenium(O) and Related Arsine Complexes

11.3.4 Tetrakis(Phosphine)Carbonylruthenium(O) and Related Arsine Complexes

11.3.5 Dimeric Species

11.4 Ruthenium(O) Complexes with Nitrogen-Donor Ligands

11.4.1 Pyridine Complexes

11.4.2 Ethanenitrile Complexes

11.5 Ruthenium(O) Isonitrile Complexes

11.6 Alkene Complexes

11.6.1 Phosphine Derivatives

11.6.2 Carbonyl Phosphine Derivatives

11.6.3 Carbonyl Derivatives

11.7 Alkyne Complexes

11.8 Diene Complexes

11.8.1 Acyclic Dienes

11.8.2 Non-Conjugated Cyclic Dienes

11.8.3 Conjugated Cyclic Dienes

11.9 Arene Complexes

11.9.1 Mono(Arene)Ruthenium(O) Complexes

11.9.2 Bis(Arene)Ruthenium(O) Complexes

11.9.3 Mixed Arene-Carbocycle Complexes

11.10 Cycloheptatriene Complexes

11.10.1 TricarbonyKcycloheptatriene)Ruthenium(O) and Related Species

11.10.2 (Cycloheptatriene)(Diene)Ruthenium(O) Complexes

11.11 Cyclooctatetraene and Cyclooctatriene Complexes

11.11.1 Tricarbonyl(Cyclooctatetraene)Ruthenium(O) and Related Species

11.11.2 (Cyclooctatetraene)(Diene)Ruthenium(O) and (Cyclooctatriene)(Diene)Ruthenium(O)

11.12 Anionic Complexes

Addenda

Chapter 12 Low Oxidation States

12.1 Sodium Tetracarbonylruthenate(-II)

12.2 Potassium Tetrakis(Trifluorophosphine)Ruthenate(-II)

Chapter 13 Ruthenium Carbonyl Clusters

13.1 Unsubstituted Carbonyl Cluster Compounds

13.1.1 Dodecacarbonyltriruthenium(3Ru-Ru)

13.1.2 Other Unsubstituted Carbonyl Compounds

13.2 Hydridocarbonyl Cluster Compounds

13.2.1 Trinuclear Hydridocarbonyl Clusters

13.2.2 Tetranuclear Hydridocarbonyl Clusters

13.2.3 Hexanuclear Hydridocarbonyl Clusters

13.3 Carbidocarbonyl Clusters

13.3.1 [Ru5C(CO)15]

13.3.2 [Ru6C(CO)17]

13.4 Halocarbonyl Clusters

13.5 Group VIB Derivatives

13.5.1 Alkoxy and Hydroxy Derivatives

13.5.2 Chalcogenide and Thiol Derivatives

13.6 Nitrene, Amine and Nitrosyl Derivatives

13.6.1 Nitrene Derivatives

13.6.2 Amine Derivatives

13.6.3 Nitrosyl Derivatives

13.7 Phosphine and Arsine Derivatives of Ruthenium Carbonyls

13.7.1 Simple Derivatives

13.7.2 Nitrosyl Derivatives

13.7.3 Hydrido Derivatives

13.7.4 Carbido Derivatives

13.8 Ethylidene, Ylid, Methylene and Germylene Derivatives

13.8.1 [H3Ru3(CO)9(CR)] {R = H or CH3}, an Ethylidyne Derivative

13.8.2 [H2Ru3(CO)10(CNMe2)], a Derivative of Ylid C=NMe2

13.8.3 [H2Ru3(CO)10(CH2)], a Methylene Derivative

13.8.4 [Ru3(CO)9(GeMe2)3], a Germylene Derivative

13.9 Alkyne Derivatives

13.9.1 Synthetic Methods

13.9.2 Structural and Spectroscopic Characterisation

13.9.3 Reactions

13.10 Alkene Derivatives

13.10.1 Acyclic Alkene Derivatives

13.10.2 Cyclic Alkene Derivatives

13.11 Allyl Derivatives

13.11.1 Acyclic allyl Derivatives

13.11.2 Cyclic allyl Derivatives

13.12 Cyclopentadienyl Derivatives

13.13 Arene Derivatives

13.14 Cycloheptatriene Derivatives

13.15 Cyclooctatetraene Derivatives

13.16 Bicyclo Derivatives

13.16.1 Pentalene Complexes

13.16.2 Azulene Complexes

13.17 Mixed-Metal Clusters

13.17.1 Trinuclear Clusters

13.17.2 Substituted Trinuclear Clusters

13.17.3 Tetranuclear Clusters

Addenda

Chapter 14 Ruthenium Nitrosyls

14.1 Ruthenium Nitrosyl Halides

14.2 Halo(Nitrosyl)Ruthenates

14.2.1 Pentahalo(Nitrosyl)Ruthenate(2-)

14.2.2 Other Salts

14.3 Aquahalo(Nitrosyl)Ruthenium Complexes, and Related Hydroxo Derivatives

14.3.1 Aquatetrahalo(Nitrosyl)Ruthenate(1-) and Hydroxotetrahalo(Nitrosyl)Ruthenate(2-)

14.3.2 Diaquatrihalo(Nitrosyl)Ruthenium

14.3.3 Triaquadihalo(Nitrosyl)Ruthenium(1+)

14.3.4 Tetraaquahalo(Nitrosyl)Ruthenium(2+)

14.4 Aqua and Hydroxo Complexes of (Nitrosyl)Ruthenium

14.4.1 Pentaaqua(Nitrosyl)Ruthenium(3+)

14.4.2 "Nitrosyl Ruthenium Hydroxide"

14.5 Nitro and Nitrato Complexes of (Nitrosyl)Ruthenium

14.5.1 Hydroxotetranitro(Nitrosyl)Ruthenate(2-)

14.5.2 Neutral Adducts of Nitro(Nitrosyl)Ruthenium and Nitrito(Nitrosyl)Ruthenium Complexes

14.5.3 Nitrato(Nitrosyl)Ruthenium Complexes, and their Hydrolysis Products

14.5.4 Nitro(Nitrato)(Nitrosyl)Ruthenium Complexes

14.6 Complexes of (Nitrosyl)Ruthenium with Anionic and Neutral Oxygen-Donor Ligands

14.6.1 Sulphato Complexes

14.6.2 β-Diketonate Complexes

14.6.3 Diolato Complexes (Quinone Derivatives)

14.6.4 Carboxylato and Oxalato Complexes

14.6.5 Complexes with Glycine and Glycolic Acid

14.6.6 Violuric and Barbituric Acid Derivatives

14.6.7 Sulphoxide Complexes

14.6.8 Heteropoly Anions

14.7 Dioxygen Complexes of (Nitrosyl)Ruthenium

14.8 Complexes of (Nitrosyl)Ruthenium with Sulphur- and Selenium-Donor Ligands

14.8.1 "Nitrosyl Ruthenium Hydrogensulphide"

14.8.2 Dithiocarbamate Complexes

14.8.3 Dithio-β-Diketonate Complexes

14.8.4 Sulphide and Selenide Complexes

14.9 Ammine(Nitrosyl)Ruthenium Complexes

14.9.1 Pentaammine(Nitrosyl)Ruthenium(3+) Salts

14.9.2 Tetraammine(Nitrosyl)Ruthenium Salts

14.9.3 Triammine(Nitrosyl)Ruthenium Salts

14.9.4 Diammine(Nitrosyl)Ruthenium Salts

14.10 Amine and Nitrile Complexes of (Nitrosyl)Ruthenium

14.11 Phosphine, Arsine and Stibine Complexes of (Nitrosyl)Ruthenium

14.11.1 Complexes of Stoicheiometry [Ru(NO)X3L2]

14.11.2 Complexes of Stoicheiometry [Ru(NO)X2L3]Y

14.11.3 Complexes of Stoicheiometry [Ru(NO)X(LL)2]Y2

14.11.4 Complexes of Stoicheiometry Ru(NO)X2L2

14.11.5 Complexes of Stoicheiometry [Ru(NO)XL2]

14.11.6 Complexes of Stoicheiometry [RU(NO)L4]Y

14.11.7 Bridging Phosphido Derivatives

14.12 Phosphine Complexes of Hydrido(Nitrosyl)Ruthenium

14.13 Carbonyl Complexes of (Nitrosyl)Ruthenium

14.13.1 Neutral Complexes

14.13.2 Cationic Complexes

14.14 Pentacyano(Nitrosyl)Ruthenate(2-) and Related Species

14.14.1 Cyanide Complexes

14.14.2 Thiocyanate Complexes

14.15 Organometallie Complexes

14.15.1 Alkyl, Acyl and Alkene Derivatives

14.15.2 Carbene Derivatives

14.15.3 Fluoroalkene Derivatives

14.15.4 Allyl Derivatives

14.16 (Nitrosyl)Ruthenium Complexes with Group IVB Donor Ligands

14.17 Dinitrosyl Ruthenium Complexes

14.17.1 Bis(Triphenylphosphine)Dinitrosylruthenium

14.17.2 Chlorobis(Triphenylphosphine)Dinitrosylruthenium(1+) Salts, and Related Hydroxo Derivatives

14.18 Arylazo and Aryldiimine Complexes

14.18.1 Arylazo Complexes

14.18.2 Aryldiimine Complexes

Chapter 15 Photophysics and Photochemistry of Tris(Diimine)Ruthenium(II) Complexes

15.1 Luminescence of Tris(2,2'-Bipyridine)Ruthenium(II) Complexes and Related Species

15.2 Electronic Absorption Spectra of Tris(2,2'-Bipyridine)Ruthenium(II) and Related Species

15.2.1 Basic Model

15.2.2 The Visible Spectrum of [Ru(Bipy)3]2+

15.2.3 The Ultraviolet Spectrum of [Ru(Bipy)3]2+

15.2.4 Theoretical Calculations on the Electronic Structure of [Ru(Bipy)3]2+

15.2.5 Spectral Tuning

15.3 Electronic Absorption and Emission Spectra of Mixed-Ligand Complexes

15.4 Spectral Properties of {[Ru(Bipy)3]2+}* and the Efficiency of Intersystem Crossing

15.5 Photolabilisation and Photochemistry of [Ru(Bipy)3]2+ and Related Complexes

15.6 Redox Potentials of Excited States and Electrogenerated Chemiluminescence

15.7 Quenching Reactions

15.7.1 Energy Transfer

15.7.2 Oxidative Quenching

15.7.3 Reductive Quenching: The Formation of [Ru(Bipy)3]+

15.8 Photocatalytic Decomposition of Water

15.8.1 The Whitten Experiment

15.8.2 The "Bouillabaisse" Technique

15.8.3 Photoassisted Electrochemical Decomposition of Water

15.8.4 Photogalvanic Cells

15.8.5 Other Photoelectrochemical Cells

Addenda

References

Addenda References

Index

Description

The Chemistry of Ruthenium is concerned with the chemistry of ruthenium, with emphasis on synthesis and structure. The discussion spans a wide range of fields, from coordination chemistry and organometallic chemistry to structural chemistry (of both molecular and extended lattices), electrochemistry and photochemistry, as well as kinetics and spectroscopy.

Comprised of 15 chapters, this book begins with an introduction to the discovery and early history of ruthenium, along with its extraction and purification, isotopes, physical and chemical properties, and applications. The discussion then turns to the concept of oxidation state and a scheme for systematizing descriptive inorganic chemistry together with its applicability to ruthenium chemistry. Subsequent chapters focus on the chemistry of ruthenium(VIII), ruthenium(VII), ruthenium(VI), ruthenium(V), ruthenium(IV), ruthenium(III), ruthenium(II), ruthenium(I), and ruthenium(0). The book also considers ruthenium carbonyl clusters and nitrosyls before concluding with a review of the photophysics and photochemistry of tris(diimine)ruthenium(II) complexes.

This monograph will be useful to students, practitioners, and researchers in the field of inorganic chemistry, as well as those who are interested in the chemistry of ruthenium.


Details

Language:
English
Copyright:
© Elsevier Science 1984
Published:
Imprint:
Elsevier Science
eBook ISBN:
9781483289908

Reviews

@qu:This is a monumental work... the authors are to be congratulated for their effort in producing a work which will undoubtedly become essential reference material for any chemist concerned with the platinum metals and probably for all transition-metal chemists. An essential acquisition for any well-stocked chemical library... @source: Journal of the American Chemical Society


About the Editors

R. J. H. Clark Editor

About the Authors

E.A. Seddon Author

Affiliations and Expertise

Daresbury Laboratory, Warrington, UK

K.R. Seddon Author

Affiliations and Expertise

The Queen's University of Belfast, Belfast, Northern Ireland