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

Organometallic molecular wires and other nanoscale-sized devices: An approach using the organoiron (dppe)Cp*Fe building block

Electronic communication in heterobinuclear organometallic complexes through unsaturated hydrocarbon bridges

Publisher Summary This chapter surveys the rapidly growing field comprising the chemistry of transition metal complexes containing ligands which are made up only of carbon atoms within their coordination spheres. The chapter describes metal complexes which contain linear or cyclic ligands of composition C n (n n ligands, in order of increasing carbon content of the ligand have been discussed. This is followed by a discussion on complexes of cyclic all-carbon ligands, such as [C 3 {Fe(CO) 2 Cp} 3 ] + . Complexes containing C n ligands associated with binuclear metal–metal bonded systems are followed by an account of metal cluster complexes containing C n ligands. It also includes hybrid complexes where a cluster supports a C n ligand also attached to a mononuclear metal–ligand fragment. The study is broadly based on a group-by-group approach and includes salient details of synthesis, properties, chemistry and electronic structure.

Transition Metal Complexes Containing All-Carbon Ligands

Ruthenium and osmium vinylidene complexes and some related compounds

Oxidized Ruthenium Ferrocenylacetylide Complexes, [(.eta.-C5H5)L2RuCCFc]PF6 and [(.eta.-C5Me5)L2RuCCFc]PF6 (L = Phosphines). Electron-Delocalized Heterobinuclear Mixed-Valence Complexes

Molecular structure and electrochemical properties of the PtII complex of 1,1′-bis(methylthio)ferrocene and the PdII complexes of 1,4,7-trithia[7]- and 1,5,9-trithia[9] (1,1′)ferrocenophanes

Double Deprotonation of a Cationic Ruthenium(II) Terminal Vinylidene Complex and Molecular Structures of the Terminal Vinylidene Complex [(η5-C5Me5)(PPh3)2Ru(CCH2)]PF6 and the Acetylide Complex (η5-C5Me5)(PPh3)2Ru(C⋮CSiMe3)

The monoynes [Rc*C[triple bond]CRc*] and [Rc'C[triple bond]CRc'] were obtained in improved yields using [Mo(CO)6]/2-FC6H5OH as a catalyst in the alkyne metathesis of [Rc*C[triple bond]CMe] and [Rc'C[triple bond]CMe], respectively (Rc = ruthenocenyl, Rc* = 1'',2'',3'',4'',5''-pentamethylruthenocenyl, and Rc' = 2',3',4',5'-tetramethylruthenocenyl groups). The diynes [Rc*(C[triple bond]C)2Rc*] and [Rc'(C[triple bond]C)2Rc'] were synthesized by the oxidative coupling of the corresponding terminal ethynes in good yields. The triyne [Rc*(C[triple bond]C)3Rc*] and the tetrayne [Rc*(C[triple bond]C)4Rc*] were prepared by the hetero- and homocoupling of [Rc*C[triple bond]CC[triple bond]CH], which was obtained from the reaction of [Rc*C[triple bond]CCHO] with Li[N2CSiMe3], respectively. Although the oxidation waves did not always exhibit a clear two-electron oxidation process, the oxidation potentials shifted to a lower potential with an increase in the number of methyl substituents on the ruthenocenyl ring, and shifted to a higher potential with the increase in the number of C[triple bond]C units; this result is in contrast to that found in the [Rc(CH=CH)(n)Rc] series. The chemical oxidation of [Rc'C[triple bond]CRc'] yielded a stable two-electron-oxidized species, the structure of which was confirmed by X-ray crystallography to be [Ru2(mu2-eta(6):eta(6)-C5Me4C=CC5Me4)(eta-C5H5)2](BF4)2. Changing the substituents (Rc, Rc*, and Rc') had no effect on the chemical oxidation, but in the case of the Rc' series the Me substituent increased the stability of the two-electron-oxidized species in solution. The diyne [Rc*(C[triple bond]C)2Rc*] and the triyne [Rc*(C[triple bond]C)3Rc*] also gave a similar but unstable two-electron-oxidized species. In acetone or acetonitrile, the two-electron-oxidized species of [Rc*C[triple bond]CRc*] and [Rc*(C[triple bond]C)2Rc*] gradually formed the corresponding bis(fulvene)-type complexes. This implies that the two-electron-oxidized species of [Rc*(C[triple bond]C)(n)Rc*] are destabilized with the increasing n.

Synthesis and Some Properties of Binuclear Ruthenocenes Bridged by Oligoynes: Formation of Bis(cyclopentadienylidene)cumulene Diruthenium Complexes in the Two‐Electron Oxidation

Yasushi Kawata

Papers

Oxidized Ruthenium Ferrocenylacetylide Complexes, [(.eta.-C5H5)L2RuCCFc]PF6 and [(.eta.-C5Me5)L2RuCCFc]PF6 (L = Phosphines). Electron-Delocalized Heterobinuclear Mixed-Valence Complexes

Molecular structure and electrochemical properties of the PtII complex of 1,1′-bis(methylthio)ferrocene and the PdII complexes of 1,4,7-trithia[7]- and 1,5,9-trithia[9] (1,1′)ferrocenophanes

Double Deprotonation of a Cationic Ruthenium(II) Terminal Vinylidene Complex and Molecular Structures of the Terminal Vinylidene Complex [(η5-C5Me5)(PPh3)2Ru(CCH2)]PF6 and the Acetylide Complex (η5-C5Me5)(PPh3)2Ru(C⋮CSiMe3)

Synthesis and Some Properties of Binuclear Ruthenocenes Bridged by Oligoynes: Formation of Bis(cyclopentadienylidene)cumulene Diruthenium Complexes in the Two‐Electron Oxidation