Outer-sphere coordination effects on the redox behaviour of the Fe(CN)63−/Fe(CN)64− couple in non-aqueous solvents

1976 ◽  
Vol 72 (2) ◽  
pp. 177-185 ◽  
Author(s):  
G. Gritzner ◽  
K. Danksagmüller ◽  
V. Gutmann
Keyword(s):  
Outer Sphere ◽  
Redox Behaviour

Flipping of the coordinated triazine moiety in Cu(i)–L2and the small electronic factor, κel, for direct outer-sphere cross reactions: syntheses, crystal structures and redox behaviour of copper(ii)/(i)–L2complexes (L = 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine)

2015 ◽  
Vol 44 (31) ◽  
pp. 13979-13990 ◽  
Author(s):  
Atsutoshi Yamada ◽  
Takuya Mabe ◽  
Ryohei Yamane ◽  
Kyoko Noda ◽  
Yuko Wasada ◽  
...  
Keyword(s):  
Crystal Structures ◽  
Outer Sphere ◽  
Triazine Ring ◽  
Electronic Factor ◽  
Cross Reactions ◽  
Redox Behaviour ◽  
Direct Cross

Flipping of the triazine ring of the coordinated pdt ligand was observed, and the non-adiabaticity factorκelfor direct cross reactions was estimated asca.10−7.

Discrete Cyanide-Bridged Mixed-Valence Co/Fe Complexes: Outer-Sphere Redox Behaviour

2003 ◽  
Vol 2003 (13) ◽  
pp. 2512-2518 ◽  
Author(s):  
Paul V. Bernhardt ◽  
Fernando Bozoglian ◽  
Brendan P. Macpherson ◽  
Manuel Martínez ◽  
Gabriel González ◽  
...  
Keyword(s):  
Mixed Valence ◽  
Outer Sphere ◽  
Redox Behaviour ◽  
Fe Complexes

Finite difference code for velocity and surface traction of a Fluid between Two Eccentric Spheres

2015 ◽  
Vol 11 (1) ◽  
pp. 2960-2971
Author(s):  
M.Abdel Wahab
Keyword(s):  
Velocity Field ◽  
Angular Velocity ◽  
Finite Difference ◽  
Numerical Study ◽  
Outer Sphere ◽  
Equation Of Motion ◽  
Annular Region ◽  
Surface Traction ◽  
Angular Velocities ◽  
Axis Passing

The Numerical study of the flow of a fluid in the annular region between two eccentric sphere susing PHP Code isinvestigated. This flow is created by considering the inner sphere to rotate with angular velocity 1  and the outer sphererotate with angular velocity 2  about the axis passing through their centers, the z-axis, using the three dimensionalBispherical coordinates (, ,) .The velocity field of fluid is determined by solving equation of motion using PHP Codeat different cases of angular velocities of inner and outer sphere. Also Finite difference code is used to calculate surfacetractions at outer sphere.

Kinetics and mechanism of redox reactions of U(III) ions with monochloroacetic and dichloroacetic acids

1979 ◽  
Vol 44 (2) ◽  
pp. 401-405 ◽  
Author(s):  
Ľubica Adamčíková ◽  
Ľudovít Treindl
Keyword(s):  
Redox Reactions ◽  
Reaction Rate ◽  
Activation Parameters ◽  
Outer Sphere ◽  
Alcohol Concentration ◽  
Kinetics And Mechanism ◽  
Solvent Structure ◽  
Influence Of Ph ◽  
Sphere Mechanism

The kinetics and mechanism of the redox reactions of U3+ ions with mono- and dichloroacetic acids were studied. The influence of pH was observed mainly in the second case and led to the determination of the rate constants and activation parameters corresponding to two parallel steps, namely oxidation of U3+ with CHCl2COO- ions and oxidation of U3+ with CHCl2.COOH molecules. The influence of binary mixtures of water with methanol, ethanol, isopropanol, or tert-butenol on the reaction rate was followed. Increasing alcohol concentration influences the rate constant not only through changing dielectric constant and solvation of the reactants but also through a change of the solvent structure which plays a role in reactions with an outer sphere mechanism of the electron transfer.

Outer-sphere interaction of (S)-asparagine and (S)-glutamine with [Co(NH3)6]3+ ion and its possible role in ligand substitution

1987 ◽  
Vol 52 (10) ◽  
pp. 2457-2459
Author(s):  
František Jursík
Keyword(s):  
Amino Acids ◽  
Transition Region ◽  
Alkaline Medium ◽  
Optical Activity ◽  
Substitution Reaction ◽  
Outer Sphere ◽  
Ligand Substitution ◽  
Cotton Effect ◽  
Negative Cotton Effect

Optical activity of the achiral cation [Co(NH3)6]3+ is induced both by (S)-AsnONa and (S)-GlnONa, as shown by a negative Cotton effect in the 1A1g → 1T1g transition region. An outer-sphere interaction by three-point attachment of the amides can explain the fact that substitution reaction of [Co(NH3)6]3+ with the mentioned amides in an alkaline medium is unusually slow as compared with other amino acids.

Protonation effects on dynamic flux properties of aqueous metal complexes

2009 ◽  
Vol 74 (10) ◽  
pp. 1543-1557 ◽  
Author(s):  
Herman P. Van Leeuwen ◽  
Raewyn M. Town
Keyword(s):  
Complex Formation ◽  
Metal Ion ◽  
Good Description ◽  
Minor Component ◽  
Outer Sphere ◽  
Metal Species ◽  
Central Metal ◽  
Inner Sphere ◽  
A Minor ◽  
Protonated Ligand

The degree of (de)protonation of aqueous metal species has significant consequences for the kinetics of complex formation/dissociation. All protonated forms of both the ligand and the hydrated central metal ion contribute to the rate of complex formation to an extent weighted by the pertaining outer-sphere stabilities. Likewise, the lifetime of the uncomplexed metal is determined by all the various protonated ligand species. Therefore, the interfacial reaction layer thickness, μ, and the ensuing kinetic flux, Jkin, are more involved than in the conventional case. All inner-sphere complexes contribute to the overall rate of dissociation, as weighted by their respective rate constants for dissociation, kd. The presence of inner-sphere deprotonated H2O, or of outer-sphere protonated ligand, generally has a great impact on kd of the inner-sphere complex. Consequently, the overall flux can be dominated by a species that is a minor component of the bulk speciation. The concepts are shown to provide a good description of experimental stripping chronopotentiometric data for several protonated metal–ligand systems.

scholarly journals RuIII(edta) complexes as molecular redox catalysts in chemical and electrochemical reduction of dioxygen and hydrogen peroxide: inner-sphere versus outer-sphere mechanism

RSC Advances ◽  
2021 ◽  
Vol 11 (35) ◽  
pp. 21359-21366
Author(s):  
Debabrata Chatterjee ◽  
Marta Chrzanowska ◽  
Anna Katafias ◽  
Maria Oszajca ◽  
Rudi van Eldik
Keyword(s):  
Hydrogen Peroxide ◽  
Electron Transfer ◽  
Electrochemical Reduction ◽  
Molecular Oxygen ◽  
Outer Sphere ◽  
Transfer Processes ◽  
Edta Complexes ◽  
Inner Sphere ◽  
Electron Transfer Processes ◽  
Sphere Mechanism

[RuII(edta)(L)]2–, where edta4– =ethylenediaminetetraacetate; L = pyrazine (pz) and H2O, can reduce molecular oxygen sequentially to hydrogen peroxide and further to water by involving both outer-sphere and inner-sphere electron transfer processes.

Features of the formation of zinc(II) and cadmium(II) complexes with the inner-sphere and outer-sphere position of the decahydro-closo-decaborate anion in the presence of azaheterocyclic ligands

2021 ◽  
Vol 520 ◽  
pp. 120315
Author(s):  
Svetlana E. Korolenko ◽  
Aleksey S. Kubasov ◽  
Lyudmila V. Goeva ◽  
Varvara V. Avdeeva ◽  
Elena A. Malinina ◽  
...  
Keyword(s):  
Outer Sphere ◽  
Inner Sphere ◽  
Closo Decaborate Anion
Sign in / Sign up

Export Citation Format

Share Document