ChemInform Abstract: KINETIC STUDIES OF LIGAND SUBSTITUTION REACTIONS AND GENERAL-BASE CATALYSIS IN AMINE-LIGAND EXCHANGE PROCESSES FOR GROUP 6B METAL CARBONYL AMINE DERIVATIVES. KINETIC AND SPECTROSCOPIC EVIDENCE FOR HYDROGEN-BONDED INTERMEDIATES

The kinetics of nucleophilic substitution reactions of 1-(phenoxycarbonyl)pyridinium ions, prepared with the essentially non-nucleophilic/non-basic fluoroborate as the counterion, have been studied using up to 1.60 M methanol in acetonitrile as solvent and under solvolytic conditions in 2,2,2-trifluoroethan-1-ol (TFE) and its mixtures with water. Under the non- solvolytic conditions, the parent and three pyridine-ring-substituted derivatives were studied. Both second-order (first-order in methanol) and third-order (second-order in methanol) kinetic contributions were observed. In the solvolysis studies, since solvent ionizing power values were almost constant over the range of aqueous TFE studied, a Grunwald–Winstein equation treatment of the specific rates of solvolysis for the parent and the 4-methoxy derivative could be carried out in terms of variations in solvent nucleophilicity, and an appreciable sensitivity to changes in solvent nucleophilicity was found.

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Physical properties, ligand substitution reactions, and biological activity of Co(iii)-Schiff base complexes

Dalton Transactions ◽

10.1039/c8dt04606a ◽

2019 ◽

Vol 48 (18) ◽

pp. 5987-6002 ◽

Cited By ~ 5

Author(s):

A. Paden King ◽

Hendryck A. Gellineau ◽

Samantha N. MacMillan ◽

Justin J. Wilson

Keyword(s):

Biological Activity ◽

Schiff Base ◽

Physical Properties ◽

Ligand Exchange ◽

Ligand Substitution ◽

Schiff Base Complexes ◽

Substitution Reactions ◽

Anticancer Properties ◽

Ligand Substitution Reactions

A subset of fluorinated Co(iii) Schiff base complexes was synthesized, and their structural, ligand exchange, and anticancer properties were investigated.

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Micellar catalysis of organic reactions. VIII. Kinetic studies of the hydrolysis of 2-acetyloxybenzoic acid (aspirin) in the presence of micelles

Australian Journal of Chemistry ◽

10.1071/ch9821357 ◽

1982 ◽

Vol 35 (7) ◽

pp. 1357 ◽

Cited By ~ 19

Author(s):

TJ Broxton

Keyword(s):

Aqueous Solution ◽

Cetyltrimethylammonium Bromide ◽

Cetylpyridinium Chloride ◽

Kinetic Studies ◽

Base Catalysis ◽

Plateau Region ◽

General Base ◽

Mechanism Of Hydrolysis ◽

Ph Range ◽

Hydrolysis Of

The hydrolysis of 2-acetyloxybenzoic acid in the pH range 6-12 has been studied in the presence of micelles of cetyltrimethylammonium bromide (ctab) and cetylpyridinium chloride (cpc). In the plateau region (pH 6-8) the hydrolysis is inhibited by the presence of micelles, while in the region where the normal BAC2 hydrolysis (pH > 9) occurs the reaction is catalysed by micelles of ctab and cpc. The mechanism of hydrolysis in the plateau region is shown to involve general base catalysis by the adjacent ionized carboxy group both in the presence and absence of micelles. This reaction is inhibited in the presence of micelles because the substrate molecules are solubilized into the micelle and water is less available in this environment than in normal aqueous solution.

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