Palladium(II) complexes of aliphatic amines and their oxidation by chloramine-T in perchloric acid medium

The formation of palladium(II) complexes with aliphatic amines and their oxidation by chloramine‐T in perchloric acid medium has been studied. The spectrophotometric studies showed the formation of 1:1 and 1:2 complexes between palladium(II) and amine in absence of HClO4. An increase in [HClO4] in r...

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Veröffentlicht in:International journal of chemical kinetics 2002, Vol.34 (10), p.603-612
Hauptverfasser: Grover, Neeti, Kambo, Neelu, Upadhyay, Santosh K.
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Upadhyay, Santosh K.
description The formation of palladium(II) complexes with aliphatic amines and their oxidation by chloramine‐T in perchloric acid medium has been studied. The spectrophotometric studies showed the formation of 1:1 and 1:2 complexes between palladium(II) and amine in absence of HClO4. An increase in [HClO4] in reaction mixture suppresses the complex formation and in presence of [HClO4] ∼10−3 mol dm−3 only a 1:1 complex between palladium(II) and amine has been observed. The effect of Cl− on the complex formation has also been studied. Palladium(II)‐catalyzed oxidation of these amines by chloramine‐T showed a first‐order dependence of rate with respect to each—oxidant, substrate, catalyst, and H+. The mechanism consistent with kinetic data for the oxidation process has been proposed in absence as well as in presence of initial [Cl−]. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 603–612, 2002
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The spectrophotometric studies showed the formation of 1:1 and 1:2 complexes between palladium(II) and amine in absence of HClO4. An increase in [HClO4] in reaction mixture suppresses the complex formation and in presence of [HClO4] ∼10−3 mol dm−3 only a 1:1 complex between palladium(II) and amine has been observed. The effect of Cl− on the complex formation has also been studied. Palladium(II)‐catalyzed oxidation of these amines by chloramine‐T showed a first‐order dependence of rate with respect to each—oxidant, substrate, catalyst, and H+. The mechanism consistent with kinetic data for the oxidation process has been proposed in absence as well as in presence of initial [Cl−]. © 2002 Wiley Periodicals, Inc. 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