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Kinetics and mechanism of oxidation of ethylenediamine and related compounds by diperiodatoargentate (III) ion
Author(s) -
Kumar Anil,
Ramamurthy P.
Publication year - 2000
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(2000)32:5<286::aid-kin4>3.0.co;2-e
Subject(s) - chemistry , ethylenediamine , kinetics , redox , ethanolamine , inorganic chemistry , reaction mechanism , substrate (aquarium) , reaction rate , medicinal chemistry , ion , deamination , catalysis , organic chemistry , physics , oceanography , quantum mechanics , enzyme , geology
The oxidation of ethylenediamine by diperiodatoargentate (III) ion has been studied by stopped‐flow spectrophotometry. Kinetics of this reaction involves two steps. The first step is the complexation of silver (III) with the substrate and is over in about 10 ms. This is followed by a redox reaction in the second step that occurs intramolecularly from the substrate to the silver (III) center. The rate of reduction of silver (III) species by ethylenediamine, ethanolamine, and 1,2‐ethanediol were observed to be 1.2 × 10 4 , 1.1 × 10 2 , and 0.14 dm 3 mol −1 s −1 , respectively, at 20°C. The reaction rate shows an inverse dependence on [IO 4 − ] and [OH − ] in the low concentration range (≤1 × 10 ‐3 mol dm −3 ). At higher [OH − ] (>1 × 10 −3 mol dm −3 ) the rate of reaction starts increasing and attains a limiting value at very high [OH − ]. The rate of deamination of ethylenediamine is enhanced by its complexation with silver (III). The involvement of [Ag III (H 2 IO 6 ) (H 2 O) 2 ] and [Ag III (H 2 IO 6 ) (OH) 2 ] 2− are suggested as the reactive silver (III) species kinetically in mild basic and basic conditions, respectively. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 286–293, 2000