Progress in Inorganic Chemistry -- Contents -- Chapter 1: Tris(dithiolene) Chemistry: A Golden Jubilee -- I. INTRODUCTION -- II. LIGANDS -- A. Arene Dithiolates -- B. Alkene Dithiolates -- 1. Sulfur -- 2. Carbon Disulfide -- 3. Phosphorus Pentasulfide -- 4. Other Sulfur Sources -- C. Dithiones -- III. COMPLEXES -- A. Metathesis -- B. Redox -- C. Transmetalation -- IV. STRUCTURES -- A. Beginnings -- 1. Neutral Complexes -- 2. Reduced Complexes -- 3. Isoelectronic Series -- B. Redux -- 1. Trigonal Twist -- 2. Dithiolene Fold -- 3. Oxidized Ligands -- V. THEORY -- A. Hückel -- B. Fenske-Hall -- VI. ELECTROCHEMISTRY -- VII. MAGNETOMETRY -- VIII. SPECTROSCOPY -- A. Vibrational -- B. Electronic -- C. Nuclear Magnetic Resonance -- D. Electron Paramagnetic Resonance -- 1. Spin Doublet -- 2. Spin Quartet -- E. X-Ray Absorption Spectroscopy -- 1. Metal Edges -- 2. Sulfur K-Edge -- F. Mössbauer -- IX. SUMMARY -- A. Group 4 (IV B) -- B. Group 5 (V B) -- C. Group 6 (VI B) -- D. Group 7 (VII B) -- E. Group 8 (VIII B) -- F. Group 9 (VIII B) and Beyond -- X. CONCLUSIONS -- ACKNOWLEDGMENTS -- ABBREVIATIONS -- REFERENCES -- Chapter 2: How to Find an HNO Needle in a (Bio)-Chemical Haystack -- I. INTRODUCTION -- A. Azanone and Its Elusive Nature -- II. CHEMICAL AND BIOLOGICAL RELEVANCE OF HNO -- A. Chemical Relevance of HNO as a Reaction Intermediate -- 1. HNO Donors -- 2. Reactions in Which Azanone Has Been Proposed As an Intermediate -- B. Azanone Biological Relevance: Friend or Foe? -- III. AZANONE DETECTION METHODS -- A. Trapping vs Real-Time Detection -- B. Colorimetric Methods -- 1. Manganese Porphyrins as Trapping Agents -- 2. Miscellaneous Colorimetric Methods -- C. Thiol Blocking -- D. Phosphines -- E. Electron Paramagnetic Resonance -- F. Mass Spectrometry -- G. Fluorescence-Based Methods -- H. Electrochemical Real-Time Detection.

IV. CONCLUSIONS AND FUTURE PERSPECTIVES -- ACKNOWLEDGMENTS -- ABBREVIATIONS -- REFERENCES -- Chapter 3: Photoactive Metal Nitrosyl and Carbonyl Complexes Derived from Designed Auxiliary Ligands: An Emerging Class of Photochemotherapeutics -- I. INTRODUCTION -- II. METAL NITROSYL AND CARBONYL COMPLEXES AS NITRIC OXIDE AND CARBON MONOXIDE DONORS -- III. PHOTOACTIVE METAL NITROSYL COMPLEXES -- A. Metal Nitrosyl Complexes With Monodentate Ligands -- B. Metal Nitrosyl Complexes Derived from Polydentate Ligands With Extended Structure -- C. Metal Nitrosyl Complexes Derived from Polydentate Ligands With Carboxamide Groups -- D. Polymer Matrices With Incorporated Metal Nitrosyl Complexes -- IV. PHOTOACTIVE METAL CARBONYL COMPLEXES -- A. Homoleptic Metal Carbonyls -- B. Metal Carbonyl Complexes With Amino Acid Ligands -- C. Manganese(I) Tricarbonyl Complexes -- D. Metal Carbonyl Complexes Derived from Polydentate Ligands -- V. CONCLUSION -- ACKNOWLEDGMENT -- ABBREVIATIONS -- REFERENCES -- Chapter 4: Metal-Metal Bond-Containing Complexes as Catalysts for C-H Functionalization -- I. INTRODUCTION -- A. Overview of Metal-Metal Multiple Bonds -- B. Early Examples of M-M Bond-Containing Complexes in Catalysis -- C. Metal-Metal Bonding -- D. Structural Manifestations of M-M Bonding -- E. Physical and Spectroscopic Properties of M-M Bond-Containing Compounds -- 1. Absorption Spectroscopy -- 2. Electron Paramagnetic Resonance Spectroscopy -- 3. Electrochemistry -- 4. Metal-Metal Bond Containing Catalyst Preparation -- II. DIRHODIUM AND DIRUTHENIUM C-H FUNCTIONALIZATION CHEMISTRY -- A. Carbenoid Chemistry -- 1. Overview of Dirhodium-Carbenoid Reactivity -- 2. Current Mechanistic Understanding of Carbenoid Chemistry -- 3. Catalyst Design, Synthesis, and General Reactivity -- 4. The Role of the M-M Bond in Dirhodium Carbenoid Species -- B. Nitrenoid Chemistry.

1. Development of Nitrenoid-Based Reactions -- 2. Synthetic Scope -- 3. Current Mechanistic Understanding and Its Impact on Catalyst Development -- C. Allylic Oxidations -- D. Diruthenium Chemistry -- III. DIPALLADIUM C-H FUNCTIONALIZATION CHEMISTRY -- A. History of Oxidative C-H Functionalization Catalyzed by Pd -- B. Catalyst Structure and Metalation Reactions -- C. Current Mechanistic Understanding -- D. Role of Binuclear Core in C-X Bond-Forming Redox Chemistry -- E. C-X Bond-Forming Reductive Elimination from Binuclear Pd(III) Complexes -- F. Unbridged Pd(III)-Pd(III) Bonds -- G. Palladium-Palladium Cleavage Pathways -- H. Dipalladium Catalysts in Aerobic Oxidation -- I. Outlook -- IV. PARALLELS BETWEEN DIRHODIUM AND DIPALLADIUM SYSTEMS -- A. Metallicity -- B. Stabilization of Unusual Oxidation States Using M-M Bonds -- C. Outlook -- V. SUMMARY -- ACNOWLEDGMENTS -- ABBREVIATIONS -- REFERENCES -- Chapter 5: Activation of Small Molecules by Molecular Uranium Complexes -- I. INTRODUCTION -- II. SCOPE AND ORGANIZATION -- III. CARBON MONOXIDE -- A. Uranium(III) Complexes -- 1. Complex [(Cp')3U(CO)] -- 2. Complex [{((tBuArO)3 tacn)U}2(μ:η1,η1-CO)] -- 3. Complex [(η8-C8H6(1,4-Si(iPr)3)2)(η5-C5Me5 nHn)U(thf)], (n = 0, 1) -- 4. Ynediolate (OCCO)2 ̄Systems -- B. Uranium(IV) Complexes -- 1. Insertion into U-C Bonds -- 2. Insertion into U=C Bonds -- 3. Insertion into U-N and U-H Bonds -- C. Uranium(V) Complexes -- 1. Complex [((AdArO)3 tacn)U(=NTMS)] -- IV. NITROGEN MONOXIDE -- A. Uranium(III) Complexes -- 1. Complex [(ODtbp)3U] -- 2. Complex [(η8-C8H6(1,4-Si(iPr)3)2)(η5-Cp*)U] -- 3. Complex [(C5Me4H)3U] -- B. Uranium (IV and V) Complexes -- 1. Complex [(N(TMS)2)3UCl] -- V. DINITROGEN -- A. Uranium(III) Complexes -- 1. Complex [{(TRENDMSB)U}2(μ,η2:η2-N2)] -- 2. Complex [{(Cp*)(η8-C8H4(1,4-Si(iPr)3)2)U}2(μ,η2:η2-N2)] -- 3. [(Cp*)3U(η1-N2)].

4. Complex [(Ar(tBu)N)3U(μ,η1:η1-N2)Mo(N(tBu)Ph)3] -- 5. Complex [{(OAr)3U}2(μ-η2:η2-N2)] -- 6. Complex [K(dme)4][K(dme){(Et8-calix[4]tetrapyrrole)U}2(μ-NK)2] -- 7. Studying N2 Cleavage Via Azide Reduction -- VI. DIOXYGEN -- A. Uranium(III) Complexes -- 1. Ligand Redistribution Reactions -- 2. Bridging Oxo Synthesis -- B. Uranium(V) Complexes -- 1. Formation of μ-Oxo and -Peroxide Ligands -- VII. CARBON DIOXIDE -- A. Uranium(III) Complexes -- 1. Reductive C=O Bond Cleavage to CO and μ-Oxo -- 2. η1-CO2 Coordination -- 3. Reductive Disproportionation to CO and CO32 ̄-- 4. Insertion into a U-C Bond -- 5. Insertion into a U-N Bond -- 6. Insertion into a U-S Bond -- B. Uranium(IV) Complexes -- 1. Insertion into a U-N Bond -- 2. Insertion into a U-C Bond -- 3. Insertion into a U-O Bond -- 4. Insertion into a U-S Bond -- C. Uranium(V) Complexes -- 1. Imido Multiple-Bond Metathesis -- VIII. NITROUS OXIDE -- A. Uranium(III) Complexes -- 1. Bridging Oxo Synthesis -- B. Uranium(IV) Complexes -- 1. Terminal Oxo Synthesis -- IX. WATER -- A. Uranium(III) Complexes -- 1. Hydroxide Synthesis -- 2. Uranyl Polymer and Cluster Synthesis -- B. Uranium(IV) Complexes -- 1. Hydroxo and Cluster Synthesis -- 2. Alkoxide Hydrolysis and Oxidation -- C. Uranium(VI) Complexes -- 1. Imido Hydrolysis -- D. Uranyl(VI/V) Complexes -- X. DIHYDROGEN -- A. Uranium(III) Complexes -- B. Uranium(IV) Complexes -- C. Uranium(VI) Complexes -- XI. SATURATED HYDROCARBONS -- A. Uranium(III) Complexes -- B. Uranium(IV) Complexes -- C. Uranium(VI) Complexes -- XII. ALKENES AND ALKYNES -- A. Uranium(III) Complexes -- 1. Reductive Coupling of Alkynes -- 2. η2-Alkyne Adduct -- 3. Terminal Alkyne Protonolysis -- B. Uranium(IV) Complexes -- 1. Terminal Alkyne Protonolysis -- 2. Alkyne and Alkene Insertion Chemistry -- 3. η2-Alkyne Adduct -- 4. [2+2] Addition and Metallacycle Formation -- XIII. ARENES.

A. Half-Sandwich Complexes -- B. Dinuclear, Inverted Sandwich Complexes -- 1. [{(Ar(R)N)2U}2(μ2-η6:η6-Arene)] -- 2. Complex [{(Mes(tBu)CN)3U}2(μ2-η6:η6-Arene)]1-2- -- 3. Complex [{(Cp*2U}2(μ2-η6:η6-Arene)] and Analogs -- 4. Complex [{(NNfc)U}2(μ2-η6:η6-C7H8)] and [{(BIPMTMSH)U(I)}2(μ2-η6:η6-C7H8)] -- 5. Complex [{(OSi(OtBu)3)3U}2(μ2-η6:η6-C7H8)] and [{(TsXyl)U}2(μ2-η6:η6-C7H8)] -- 6. Complex [{(X)2U}2(μ2-η6:η6-Arene)] and Arene C-H Borylation -- C. Benzyne -- XIV. CONCLUDING REMARKS -- ACKNOWLEDGMENTS -- ABBREVIATIONS -- REFERENCES -- Chapter 6: Reactive Transition Metal Nitride Complexes -- I. INTRODUCTION -- II. SCOPE -- III. PREVIOUS REVIEWS -- IV. PROPERTIES OF THE NITRIDE LIGAND -- A. Simple Bonding Considerations -- B. Structural and Electronic Impact of the Nitride Ligand -- C. Effects of Orbital Mixing -- D. Bonding Analogies -- E. Noninnocence of the Nitride Ligand -- V. SYNTHESIS OF TRANSITION METAL NITRIDES -- A. Azide Decomposition -- B. Ammonia Oxidation -- C. Nitrogen-Atom Transfer -- D. Cleavage of N-Si Bonds -- E. Reductive Cleavage of N2 -- F. Cleavage of N-N Bonds -- G. Cleavage of C-N Bonds -- H. Nitrosyl Deoxygenation -- I. Cleavage of N2O N-N Bond -- J. Other N-E Cleavage Reactions -- VI. REACTIVITY -- A. Three-Electron Reactions -- 1. Intermetallic Nitrogen-Atom Transfer -- 2. Reductive Coupling -- B. Two-Electron Reactions -- 1. Intermetallic Nitrogen-Atom Transfer -- 2. Reaction With Phosphines -- 3. Reaction With CO, CNR, CN ̄, and Carbenes -- 4. Reaction With Carbanions -- 5. Formation of Nitrosyl, Thionitrosyl, and Selenonitrosyl Ligands -- 6. Reaction With Amines -- 7. Reaction With Azide -- 8. Reaction With Thiols -- 9. Reaction With Nitriles -- 10. Reaction With Alkenes -- C. One-Electron Reactions -- D. Reactions With No Change in Oxidation State -- 1. Reaction With CO2 and CS2 -- 2. Reaction With Lewis Acids.

3. Reaction With Alkylating and Acylating Reagents.