The Chemistry of Ruthenium

FrontispieceAbbreviationsSign Conventions and Conversion FactorsChapter 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 RutheniumChapter 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 SpectroscopyChapter 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 AddendaChapter 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 AddendaChapter 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) AddendaChapter 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 AddendaChapter 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 AddendaChapter 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 AddendaChapter 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 AddendaChapter 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 AddendaChapter 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 AddendaChapter 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(