Search results for "Oxidation state"
showing 10 items of 91 documents
ChemInform Abstract: Transition Metal Derivatives of Low Oxidation State Phosphorus Oxoacids: Synthetic Pathways and Structural Studies
2010
Abstract A general synthetic approach intended to rationalize the solution preparative chemistry of transition metal phosphites and hypophosphites is presented. As previously shown for other derivatives containing also tetrahedral or pseudotetrahedral oxoanions, the hydrolytic processes affecting the cationic moieties play a determinant role on the very nature of the final solid. In fact, despite the limited number of donor atoms in the anions, the crystal chemistry of these compounds is quite intricate because of both the variety of possible cationic aggregates and the many ways to interconnect them through pseudotetrahedral anionic groups.
The Pd3(dppm)3(CO)n clusters (n = 1-,2-); rare cases of anionic palladium species.
2010
Two novel anionic palladium clusters, Pd(3)(dppm)(3)(CO)(n-) (Pd(3)(n); n = 1-,2-) were electrochemically generated from the dicationic cluster Pd(3)(2+) in 0.2 M THF/Bu(4)NPF(6)via two first consecutive reversible 1-electron reductions (Pd(3)(2+) + 1 e(-) ⇌ Pd(3)(+), -0.210, and Pd(3)(+) + 1 e(-) ⇌ Pd(3)(0), -0.470 V vs. SCE) followed by two others at -2.350 (Pd(3)(0) + 1 e(-) ⇌ Pd(3)(1-), reversible) and at -2.690 V vs. SCE (Pd(3)(1-) + 1 e(-) ⇌ Pd(3)(2-), irreversible). The chemical stability and instability, respectively, of the Pd(3)(dppm)(3)(CO)(n-) clusters (Pd(3)(n); n = 1-,2-) at the time scale of the electrochemical experiments were addressed by DFT computations. Indeed, geometry …
Towards Molecular Conductors with a Spin‐Crossover Phenomenon:Crystal Structures, Magnetic Properties and Mössbauer Spectra of[Fe(salten)Mepepy][M(dm…
2005
Three new iron(III) compounds of formula [Fe(salten)Mepepy][M(dmit)2]·CH3CN (M = Ni, Pd, Pt; H2salten = 4-azaheptamethylene-1,7-bis(salicylideneiminate); Mepepy = 1-(pyridin-4-yl)-2-(N-methylpyrrol-2-yl) ethane; dmit2– = 1,3-dithiole-2-thione-4,5-dithiolato) have been synthesised and the crystal structure of each compound has been solved at different temperatures. The structures consist of alternating layers of [M(dmit)2]– units and [Fe(salten)Mepepy] cations. In the Ni compound photo-isomerisation of the Mepepy ligand can be observed in dichloromethane solution. The temperature dependence of the magnetic susceptibility of the compounds reveals a gradual S = 5/2 blabla S = 1/2 spin crossove…
Migration Reactivities of σ-Bonded Ligands of Organoiron and Organocobalt Porphyrins Depending on Different High Oxidation States
1999
Migration reactivities of sigma-bonded organo-iron and -cobalt porphyrins were examined as a function of the compound oxidation state. Migration rates were determined for both the one-electron and two-electron oxidized species produced in the electron-transfer oxidation with different oxidants in acetonitrile at 298 K. The investigated compounds are represented as [(OETPP)Fe(R)](n)()(+), where n = 1 or 2, OETPP = the dianion of 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin, and R = C(6)H(5), 3,5-C(6)F(2)H(3), or C(6)F(5), and as [(TPP)Co(R)](n)()(+), where n = 1 or 2, TPP = the dianion of 5,10,15,20-tetraphenylporphyrin, and R = CH(3) or C(6)H(5). The rapid two-electron oxid…
Zinn - Chalkogen - Heterocyclen. V. 2,2,3,3,5,5,6,6-Octamethyl-1.4-dithia-2,3,5,6-tetpastan-ninan, Darstellung und Zersetzung eines Zinnreichen Heter…
1977
Abstract The title compound can be regarded as a sulfur derivative of the corresponding organoditin compound arid contains -formally- tin in the oxidation state 3. It is prepared in analogy to tris (dimethyltinsulfide).
Au deposited on CeO2 prepared by a nanocasting route: A high activity catalyst for CO oxidation
2014
Abstract A set of catalysts comprised of gold on different CeO 2 supports has been prepared by a nanocasting route and characterized by several physicochemical techniques. These catalysts have been tested for CO oxidation and show outstanding catalytic activity. Higher calcination temperatures of the hard template, producing a poorly ordered silica template, have led to a higher amount of oxygen vacancies on the surface of CeO 2 . The presence of surface oxygen defects in the support combined with the deposition of Au nanoparticles ( ca. 3 nm) homogeneously dispersed on the CeO 2 support may explain the excellent behaviour for low temperature CO oxidation. Surprisingly, it has been observed…
2-Tetrahydrofurfuroxo-vanadium-(III) and -(IV) complexes. Synthesis, structures and reactivities of [V2Mg2(μ3,δ2-thffo)2(μ,δ2-thffo)4Cl4]· 2CH2Cl2 an…
1997
Vanadium complexes of 2-tetrahydrofurfuroxide (2-tetrahydrofurylmethoxide) (thffo) with the metal in oxidation state III and IV have been prepared and characterized. The reaction of [VCl3(thf)3] with 1.5 equivalents of [Mg(thffo)2] in tetrahydrofuran (thf) or CH2Cl2 led to the formation of [V2Mg2(µ3,η2-thffo)2(µ,η2-thffo)4Cl4]· 2CH2Cl21. Its structure consists of centrosymmetric tetranuclear molecules and CH2Cl2 of crystallization. Two Mg and two V atoms have distorted octahedral geometry and form a nearly regular Mg2V2 rhombus. The V · · · V distance is 3.266(2) A. The reaction of [VOCl2(thf)2] with Na(thffo) in thf yielded [V2(µ,η2-thffo)2Cl2O2] 2. Two VOCl units are linked by alkoxide ox…
Molybdenum Clusters on a TiO2(110) Substrate Studied by Density Functional Theory.
2009
International audience; A theoretical study on molybdenum clusters adsorbed on a rutile TiO2(110) substrate is reported. Using density functional theory, equilibrium geometries, atomic charges, and total energies have been calculated for clusters containing up to five Mo atoms. Isolated Mo adatoms are strongly oxidized and repel each other. The Mo oxidation state is considerably lowered as soon as the first short Mo−Mo bond is formed. The relative stability of different cluster geometries can be understood from the competition between Mo−Mo and Mo−O bonding. Some low-energy structures for two and three Mo atoms involve large displacements of a substrate oxygen atom. The most stable five-ato…
High oxidation state aqueous organometallics: synthesis and structure of a dinuclear oxo(pentamethylcyclopentadienyl)acetato complex of molybdenum(IV…
2003
International audience; The zinc reduction of Cp*2Mo2O5 in a MeOH–H2O mixture in the presence of acetic acid affords the diamagnetic dinuclear compound [Cp*MoO(O2CCH3)]2. An X-ray structural investigation reveals a novel dioxo- and diacetato-bridged structure, with a relatively strong metal–metal bond [2.5524(3) Å]. The compound exhibits a reversible one-electron oxidation process in the cyclic voltammogram. A comparison with other related structures reveals the effect of the electric charge on the mononuclear or dinuclear structural choice.Zinc reduction of Cp*2Mo2O5 in water–methanol in the presence of acetic acid affords compound Cp*2Mo2O2(O2CCH3)2, whose dinuclar tetrabridged structure …
The oxidation state of iron in silicic melt at 500 MPa water pressure
2002
Abstract The dependence of the ferric–ferrous ratio in silicate melts on oxygen fugacity was studied in the system SiO2(Qz)–NaAlSi3O8(Ab)–CaAl2Si2O8(An)–H2O using Mossbauer spectroscopy. Experiments were performed under water-saturated conditions at 500 MPa, and at temperatures of 850 and 950 °C, covering a range typical for magmatic processes. The oxygen fugacity was varied in the fO2 range from Cu–Cu2O buffer to slightly more reducing conditions than the wustite–magnetite buffer. The iron redox ratio was determined by analyzing the Mossbauer parameter distribution that was modeled based on experimental spectra collected at room temperature on the quenched samples. The obtained iron redox …