Intramolecular Trapping of an Intermediate in the Reduction of Imines by a Hydroxycyclopentadienyl Ruthenium Hydride:  Support for a Concerted Outer Sphere Mechanism

2007 ◽  
Vol 129 (38) ◽  
pp. 11821-11827 ◽  
Author(s):  
Charles P. Casey ◽  
Timothy B. Clark ◽  
Ilia A. Guzei
Keyword(s):  
Outer Sphere ◽  
Ruthenium Hydride ◽  
Hydroxycyclopentadienyl Ruthenium Hydride ◽  
Sphere Mechanism

Hydrogenation of Benzonitrile to Benzylamine Catalyzed by Ruthenium Hydride Complexes with P−NH−NH−P Tetradentate Ligands:  Evidence for a Hydridic−Protonic Outer Sphere Mechanism

2007 ◽  
Vol 26 (24) ◽  
pp. 5940-5949 ◽  
Author(s):  
Tianshu Li ◽  
Ines Bergner ◽  
F. Nipa Haque ◽  
Marco Zimmer-De Iuliis ◽  
Datong Song ◽  
...  
Keyword(s):  
Outer Sphere ◽  
Ruthenium Hydride ◽  
Hydride Complexes ◽  
Tetradentate Ligands ◽  
Sphere Mechanism

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.

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.

scholarly journals Dy-DOTA integrated mesoporous silica nanoparticles as promising ultrahigh field magnetic resonance imaging contrast agents

Nanoscale ◽  
2018 ◽  
Vol 10 (45) ◽  
pp. 21041-21045 ◽  
Author(s):  
Xiao-Yu Zheng ◽  
Juan Pellico ◽  
Alexandr A. Khrapitchev ◽  
Nicola R. Sibson ◽  
Jason J. Davis
Keyword(s):  
Magnetic Resonance Imaging ◽  
Mesoporous Silica ◽  
Mesoporous Silica Nanoparticles ◽  
Silica Nanoparticle ◽  
Outer Sphere ◽  
Resonance Imaging ◽  
Mesoporous Silica Nanoparticle ◽  
Ultrahigh Field ◽  
Magnetic Resonance Imaging Contrast ◽  
Sphere Mechanism

Integrating Dy-DOTA motifs into mesoporous silica nanoparticle scaffolds significantly amplifies the ultrahigh field T2 relaxivity via a Curie outer-sphere mechanism.

Mechanism of Zn(OTf)2catalyzed hydroamination–hydrogenation of alkynes with amines: insight from theory

2017 ◽  
Vol 41 (12) ◽  
pp. 5082-5090 ◽  
Author(s):  
Riffat Un Nisa ◽  
Khurshid Ayub
Keyword(s):  
Transition Metals ◽  
Outer Sphere ◽  
Late Transition Metals ◽  
Late Transition ◽  
Sphere Mechanism

Zn(OTf)2catalyzed hydroamination of alkynes with amines proceeds through an outer sphere mechanism which is contrary to other late transition metals.

scholarly journals Synthesis and Oxidation ofCobalt(II) Pheophytin-α Complex

2011 ◽  
Vol 8 (s1) ◽  
pp. S297-S303 ◽  
Author(s):  
Ezekiel D. Dikio ◽  
David A. Isabirye
Keyword(s):  
Metal Ion ◽  
Oxidation Reaction ◽  
Dilute Hydrochloric Acid ◽  
Outer Sphere ◽  
Central Metal ◽  
First Order ◽  
First Order Kinetics ◽  
Mechanism Of Oxidation ◽  
Absorption Transitions ◽  
Sphere Mechanism

The mechanism of oxidation of natural pheophytin-aincorporated with cobalt as the central metal ion has been investigated. Natural pheophytin-aextracted from spinach was metallated with cobalt(II) to form the complex, cobalt(II) pheophytin-α[Cophe]. The complex was characterized by Ultraviolet and Visible, Fourier Transform Infrared and Electrospray ion Mass Spectroscopy. The synthesis of cobalt(II) pheophytin-awas carried out and the effect of the substitution on the chlorophyll macrocycle was studied by the reaction of hexaaquachromium(III) cation. The presence of cobalt as the central metal ion increases the energies of the chlorophyll main absorption transitions. The oxidation of the cobalt(II) pheophytin-α, [Cophe] by hexaaquachromium(III) cation in dilute hydrochloric acid has been studied and found to follow first-order kinetics. Rate constants for the oxidation reaction at 313, 322.8 and 332.9 K were found to be 5.4×10-5, 1.8×10-4and 5.9×10-4/s respectively. An outer-sphere mechanism has been proposed for the oxidation of cobalt(II) pheophytin-α.

Oxidation of low-spin iron(II) porphyrins by molecular oxygen. An outer sphere mechanism

Biochemistry ◽  
1978 ◽  
Vol 17 (3) ◽  
pp. 481-486 ◽  
Author(s):  
Margaret M. L. Chu ◽  
C. E. Castro ◽  
G. M. Hathaway
Keyword(s):  
Molecular Oxygen ◽  
Outer Sphere ◽  
Sphere Mechanism
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