1. Advantages of Chemical Redox Agents 878 2. Disadvantages of Chemical Redox Agents 879 C. Potentials in Nonaqueous Solvents 879 D. Reversible vs Irreversible ET Reagents 879 E. Categorization of Reagent Strength 881 II. Oxidants 881 A. Inorganic 881 1. Metal and Metal Complex Oxidants 881 2. Main Group Oxidants 887 B. Organic 891 1. Radical Cations 891 2. Carbocations 893 3. Cyanocarbons and Related Electron-Rich Compounds 894

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Chemical Redox Agents for Organometallic Chemistry

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The localized-to-delocalized transition in mixed-valence chemistry.

In our information-rich world, it is becoming increasingly important to develop technologies capable of displaying dynamic and changeable data, for reasons ranging from value-added advertising to environmental sustainability. There is an intense drive at the moment towards paper-like displays, devices having a high reflectivity and contrast to provide viewability in a variety of environments, particularly in sunlight where emissive or backlit devices perform very poorly. The list of possible technologies is extensive, including electrophoretic, cholesteric liquid crystalline, electrochromic, electrodewetting, interferometric and more. Despite tremendous advances, the key drawback of all these existing display options relates to colour. As soon as an RGB (red, green and blue) colour filter or spatially modulated colour scheme is implemented, substantial light losses are inevitable even if the intrinsic reflectivity of the material is very good.

Photonic-crystal full-colour displays

Organometallic Polymers with Transition Metals in the Main Chain.

The appearance of ferrocene in the middle of the 20th century has revolutionized organometallic chemistry and is now providing applications in areas as varied and sometimes initially unexpected as optical and redox devices, battery and other materials, sensing, catalysis, including asymmetric and enantioselective catalysis, and medicine. The author presents here a general, although personal, view of ferrocene's chemistry, properties, functions, and applications through a literature survey involving both historical and up-to-date trends and including examples of his group's research in a number of these areas. The review gathers together general features of ferrocene chemistry and representative examples of the salient aspects. Its focus is on ferrocene's basic properties, ferrocene-containing ligands, the ferrocene/ferricinium redox couple, ferrocene mixed-valence and average-valence systems, the ferricinium/ferrocene redox shuttle in catalysis, ligand-exchange reactions, ferrocene-containing polymers, ferrocene-containing structures for cathodic battery and other materials, ferrocenes in supramolecular ensembles, liquid crystals, and nonlinear optical materials, ferrocene-containing stars and their electrostatic effects, ferrocene-containing dendrons, dendrimers, and nanoparticles (NPs) and their application in redox sensing and catalysis, and ferrocenes in nanomedicine.

Why is Ferrocene so Exceptional

In order to gain insight into the electrochemical and conformational properties of the prototypical high polymeric poly(ferrocenylsilane), poly(ferrocenyldimethylsilane) [Fe(η-C5H4)2SiMe2]n 6, three series of oligo(ferrocenylsilanes) R-fc-[SiMe2-fc]n-1-R‘ (fc = Fe(η-C5H4)2) 72−79 (R = R‘ = H), 82−87 (R = H and R‘ = SiMe3), and 92−97 (R = R‘ = SiMe3) have been prepared and studied (the subscript n in the oligomer refers to the number of ferrocene units present). These species were prepared via the anionic ring-opening oligomerization of the silicon-bridged [1]ferrocenophane Fe(η-C5H4)2SiMe2 5. Initiation with ferrocenyllithium FcLi (Fc = Fe(η-C5H5)(η-C5H4)) followed by quenching with H2O or SiMe3Cl afforded H-fc-[SiMe2-fc]n-1-H (72-9) or H-fc-[SiMe2-fc]n-1-SiMe3 (82-7), respectively. Initiation with the dilithioferrocene complex fcLi·2/3TMEDA followed by quenching with H2O or SiMe3Cl similarly afforded the oligomers H-fc-[SiMe2-fc]n-1-H (72-9) or alternatively the bis(silyl)-capped species Me3Si-fc-[SiMe2-...

Linear Oligo(ferrocenyldimethylsilanes) with between Two and Nine Ferrocene Units: Electrochemical and Structural Models for Poly(ferrocenylsilane) High Polymers

The oxidative electron-transfer properties of several superphane complexes consisting of cyclopentadienylcobalt cyclobutadiene moieties linked by either three (compounds 1 and 4) or five (compounds 2 and 5) bridging methylene groups have been studied by experimental and theoretical methods In both cases two separate one-electron oxidations are found The mixed-valent monocations of the (−CH2−)5-bridged complexes are valence-trapped with very weak interactions between metal centers The (−CH2−)3 complexes, however, have strong interactions between the two molecular halves The intervalence transfer (IT) band of 1+ has characteristics of both class II (localized) and class III (delocalized) behavior, but the IR spectra of carboxy-labeled 4+ clearly establish trapped valence for the monocations of the propano-bridged systems Photoelectron spectra and ab initio calculations at the UHF level show that, in the ground electronic state, 1+ has a half-filled orbital (ie, electron spin) that is essentially loca

Transannular Effects in Dicobalta−Superphane Complexes on the Mixed-Valence Class II/Class III Interface: Distinguishing between Spin and Charge Delocalization by Electrochemistry, Spectroscopy, and ab Initio Calculations

Two-Electron and One-Electron Reduction of the Indenyl Complex [Mn(.eta.5-C9H7)(CO)3] and Reversible Counterion-Controlled Comproportionation of [Mn(.eta.5-C9H7)(CO)3] and [Mn(.eta.3-C9H7)(CO)3]2- To Give [Mn(.eta.5-C9H7)(CO)3]-

Sherri R. Lovelace

Papers

Linear Oligo(ferrocenyldimethylsilanes) with between Two and Nine Ferrocene Units: Electrochemical and Structural Models for Poly(ferrocenylsilane) High Polymers

Transannular Effects in Dicobalta−Superphane Complexes on the Mixed-Valence Class II/Class III Interface: Distinguishing between Spin and Charge Delocalization by Electrochemistry, Spectroscopy, and ab Initio Calculations

Two-Electron and One-Electron Reduction of the Indenyl Complex [Mn(.eta.5-C9H7)(CO)3] and Reversible Counterion-Controlled Comproportionation of [Mn(.eta.5-C9H7)(CO)3] and [Mn(.eta.3-C9H7)(CO)3]2- To Give [Mn(.eta.5-C9H7)(CO)3]-

Infrared Spectroelectrochemistry of Boron-Hydrogen Stretches: A Tool for Diagnosis of Delocalization in Mixed-Valent Metallacarborane Complexes

Synthesis and Properties of the 17-Electron, Tantalum-Centered Radical Ta(CO)4(Ph2PCH2CH2PPh2)