Role of Explicit Solvents in Palladium(II)-Catalyzed Alkoxylation of Arenes: An Interesting Paradigm for Preferred Outer-Sphere Reductive Elimination over Inner-Sphere Pathway

2012 ◽  
Vol 31 (17) ◽  
pp. 6466-6481 ◽  
Author(s):  
Megha Anand ◽  
Raghavan B. Sunoj
Keyword(s):  
Outer Sphere ◽  
Reductive Elimination ◽  
Inner Sphere

Outer-sphere and inner-sphere processes in reductive elimination. Direct and indirect electrochemical reduction of vicinal dibromoalkanes

1990 ◽  
Vol 112 (17) ◽  
pp. 6162-6177 ◽  
Author(s):  
Doris Lexa ◽  
Jean Michel Saveant ◽  
Hans J. Schaefer ◽  
Su Khac Binh ◽  
Birgit Vering ◽  
...  
Keyword(s):  
Electrochemical Reduction ◽  
Outer Sphere ◽  
Reductive Elimination ◽  
Inner Sphere

Role of carboxylic and phenolic groups in NOM adsorption on minerals: a review

2006 ◽  
Vol 6 (6) ◽  
pp. 155-164 ◽  
Author(s):  
X.H. Guan ◽  
D.L. Li ◽  
C. Shang ◽  
G.H. Chen
Keyword(s):  
Organic Matter ◽  
Aluminium Hydroxide ◽  
Interaction Strength ◽  
Outer Sphere ◽  
Hydroxyl Groups ◽  
Aromatic Carboxylates ◽  
Inner Sphere ◽  
Outer Sphere Complexes ◽  
Inner Sphere Complexes

This paper presented the current state of our understanding of the roles of carboxylic and phenolic groups in NOM adsorption and reviewed the contradictory opinions in the literatures. Previous studies carried out by other researchers indicated that aromatic carboxylates were adsorbed onto metal (hydr)oxides via outer-sphere complexes under most conditions and phenolic groups were very crucial for formation of inner-sphere complexes between organic acids and metal (hydr)oxides. Adsorption test with in-situ ATR-FTIR spectroscopic investigation were carried out to verify the role of aromatic carboxylic and phenolic groups in the NOM adsorption onto aluminium hydroxide surfaces by using a series of aromatic carboxylic acids and dihydroxybenzoic acids as the surrogate of NOM. Our studies suggested that the formation of outer-sphere complexes dominated the adsorption of most of the aromatic carboxylates over the pH range of 5–9; inner-sphere complexes were only detected at some pH levels for some aromatic carboxylates adsorption; and the aromatic carboxylates were most likely to be adsorbed to the first surface layer of hydroxyl groups and water molecules without forming coordinative bonds with the aluminium hydroxide surfaces but strong hydrogen bonds were formed in this process. Our study also revealed that (1) the presence of phenolic groups can increase the interaction strength of carboxylate groups with aluminium hydroxide; (2) chelate formation involving a carboxylate oxygen atom and ortho-phenolic-oxygen is important for the adsorption of organic matter on aluminium hydroxide at acidic pH; and 3) the phenolic groups adjacent to each other are more important than the carboxylic groups at alkaline pH for organic matter adsorption.

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
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