Search results for "Stability"
showing 10 items of 3085 documents
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 …
Addressing selectivity criteria in binding equilibria
2012
Abstract Chemical systems, in particular those involving biological and environmental backgrounds, develop through selective processes which are determined by multiple equilibria. Several methods that have been developed to assess thermodynamic selectivity in binding equilibria, including the analysis of selectivity coefficients, the use of calculated species distribution diagrams, selectivity diagrams, and conditional stability constants, are reviewed in this paper with reference to examples mainly related to chemical systems of biological and/or environmental concern. Also the concept of binding affinity has been dealt with, since binding selectivity in equilibrium systems relates to the …
Kinetic and thermodynamic stability of the group 13 trihydrides.
2009
The kinetic and thermodynamic stabilities of the group 13 hydrides EH(3) (E = B, Al, Ga, In, Tl, E113) are investigated by relativistic density functional and wave function based theories. The unimolecular decomposition of EH(3) --EH + H(2) becomes energetically more favorable going down the Group 13 elements, with the H(2)-abstraction of InH(3), TlH(3), and (E113)H(3) (E113: element with nuclear charge 113) being exothermic. In accordance with the Hammond-Leffler postulate, the activation barrier for the dissociation process decreases accordingly going down the group 13 elements in the periodic table shifting to an early transition state, with activation energies ranging from 88.4 kcal/mol…
Thermal and Light-Induced Spin Transition in the High- and Low-Temperature Structure of [Fe0.35Ni0.65(mtz)6](ClO4)2
1996
The thermal and light induced spin transition in [Fe(0.35)Ni(0.65)(mtz)(6)](ClO(4))(2) (mtz = 1-methyl-1H-tetrazole) was studied by (57)Fe Mössbauer spectroscopy and magnetic susceptibility measurements. In addition to the spin transition of the iron(II) complexes the compound undergoes a structural phase transition. The high-temperature structure could be determined by X-ray crystallography of the isomorphous [Fe(0.25)Ni(0.75)(mtz)(6)](ClO(4))(2) complex at room temperature. The X-ray structural analysis shows this complex to be rhombohedric, space group Rthremacr;, with a = 10.865(2) Å and c = 23.65(1) Å with three molecules in the unit cell. The transition to the low-temperature structur…
Compressibility and Structural Stability of Nanocrystalline TiO2 Anatase Synthesized from Freeze-Dried Precursors
2014
The high-pressure structural behavior of 30 nm nanoparticles of anatase TiO2 was studied under hydrostatic and quasi-hydrostatic conditions up to 25 GPa. We found that the structural sequence is not sensitive to the use of different pressure transmitting media. Anatase-type nanoparticles exhibit a phase transition beyond 12 GPa toward a baddeleyite-type structure. Under decompression this phase transition is irreversible, and a metastable columbite-type structure is recovered at ambient conditions. The bulk modulus of anatase-type nanoparticles was determined confirming that nanoparticles of TiO2 are more compressible than bulk TiO2. Similar conclusions were obtained after the determination…
(NBu4)Ni(mnt)2: A novel bistable high temperature spin-Peierls-like system
2005
Abstract The title compound, tetrabutylammonium bis(1,2-dimercaptoethene-1,2-dicarbonirtilato-S,S′)-nickel (III) [henceforth (NBu4)Ni(mnt)2] undergoes a hysteretic phase transition that occurs at 172 K upon cooling. Crystallographic studies show that the phase transition is an order–disorder type involving one arm of the NBu 4 + cation. Both phases are monoclinic, space group C2/c with a = 30.860(3), b = 13.804(2), c = 15.678(2) A and β = 115.642(3)° with V = 6020.8(11) A3 at room temperature and with a = 31.073(3), b = 13.928(1), c = 14.414(1) A and β = 115.073(2)° and V = 5652.1(9) A3 at 84 K. In both phases, the anions form non-uniform stacks parallel to the crystallographic c direction.…
Complexes of organometallic compounds. XXXVIII. Anion Exchange Studies on the Trimethyllead (IV) Thiocyanate aqueous complex system
1974
The distribution of Me3PbIV between the anion exchange resin Dowex 1 X 8 and aqueous solutions of NaSCN and KSCN was investigated. In the aqueous phase, up to 3 M thiocyanate concentration, only the formation of the neutral species Me3PbNCS was detected and the related stability constant evaluated. Evidence of formation into the resin phase of the anionic Me3Pb(NCS) species was obtained.
Ethylene polymerization by the thermally unique 1-[2-(bis(4-fluoro phenyl)methyl)-4,6- dimethylphenylimino]-2-aryliminoacenaphthylnickel precursors
2015
A series of 1-[2-(bis(4-fluorophenyl)methyl)-4,6-dimethylphenylimino]-2-aryliminoacenaphthylene derivatives together with the corresponding nickel bromide complexes was synthesized and characterized. Representative complexes C2 and C5 were characterized by the single-crystal X-ray diffraction, revealing a distorted tetrahedral geometry. Upon activation with either methylaluminoxane (MAO) or ethylaluminum sesquichloride (EASC), all nickel complexes exhibited high activities towards ethylene polymerization, producing polyethylene with a relatively low degree of branching and narrow polydispersity. Complex C1 maintained good activity at elevated reaction temperatures, which indicates significa…
Phenolate complexes of iron(III) in dimethylsulphoxide solution
1984
The formation of complexes between Fe3+ and 2,4-dinitrophenol, 4-nitrophenol and 4-methylphenol is studied in dimethylsulphoxide solution. The reaction proceeds almost to completion and the occurrence, in solution, of complexes with higher stoichiometry than 1∶1 is reported for the first time. The following stability constants are determined (25 °C, 0.1 M KClO4): FeIII-2,4-dinitrophenolate β1=1.8×103, β2=4.4×105; FeIII-4-nitrophenolate β1=1.10×107, β2=2.5×1012 β3=3.9×1016; FeIII-4-methylphenolate β=1.7×1012.
Decomposition studies of group 6 hexacarbonyl complexes. Part 1: Production and decomposition of Mo(CO)6 and W(CO)6
2015
Abstract Chemical studies of superheavy elements require fast and efficient techniques, due to short half-lives and low production rates of the investigated nuclides. Here, we advocate for using a tubular flow reactor for assessing the thermal stability of the Sg carbonyl complex – Sg(CO)6. The experimental setup was tested with Mo and W carbonyl complexes, as their properties are established and supported by theoretical predictions. The suggested approach proved to be effective in discriminating between the thermal stabilities of Mo(CO)6 and W(CO)6. Therefore, an experimental verification of the predicted Sg–CO bond dissociation energy seems to be feasible by applying this technique. By in…