Kinetics of Multidentate Ligand-substitution Reactions. XVIII. Substitution Reactions of Triethylenetetraaminehexaacetate (TTHA) with Nickel(II)–Dien, –EDMA, and –NTA Complexes

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概要

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• The kinetics of the substitution reactions of TTHA with nickel(II) complexes of diethylenetriamine (Dien), ethylenediaminemonoacetate (EDMA), and nitrilotriacetate (NTA) were studied systematically by employing the polarographic technique. All the substitution reactions were found to have a common reaction mechanism. They were first-order with respect to TTHA and also first-order with respect to a 1:1-ratio nickel(II) complex of Dien, EDMA, or NTA. In all the substitution reactions, the rate constants for the reactions involving a com-pletely-deprotonated TTHA anion were nearly identical to those for the corresponding DTPA (diethylenetriaminepentaacetate) reactions, suggesting that the TTHA reaction has the same reaction mechanism as the DTPA reaction. In the Dien system, the rate constant for the reaction of the quadrivalent TTHA anion is nearly identical to that of the quinquivalent TTHA anion, whereas, in the reactions of NTA and EDMA complexes, the reaction of the quadrivalent TTHA anion is drastically slower than that of the quinquivalent TTHA anion. These facts suggest that the proton transfer from the entering group to the leaving group plays an important role in determining the rate of the multidentate ligand-substitution reaction.

• 公益社団法人 日本化学会の論文

著者

• Kodama Mutsuo

  Department Of Chemistry College Of General Education Hirosaki University

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