Kinetics of the Ligand Substitution Reaction of the Copper(II)-4-(2-Pyridylazo)resorcinol Complex with (Ethylene glycol)-bis(2-aminoethyl ether)-<I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tetraacetic Acid
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概要
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The kinetics of the ligand substitution reaction of the copper(II)-4-(2-pyridylazo)resorcinol complex (Cu(II)-PAR) with (ethylene glycol)bis(2-aminoethyl ether)-<I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tetraacetic acid (EGTA) has been studied spectrophotometrically at pH 9–10 at μ=0.10 (NaClO<SUB>4</SUB>) and at 25.0°C. The reaction proceeds through the 1:1 Cu(II)-PAR complex resulting from the predissociation equilibrium of the 1:2 Cu(II)-PAR complex:<BR>-d[CuR_2^2-]/dt=10^6.15[CuR_2^2-][H^+][Y']/[HR^-]=10^2.9[CuR][Y'] <BR>where R<SUP>2</SUP>- refers to the divalent anion of PAR (H<SUB>2</SUB>R) and Y′ the free EGTA not combined with any metal. The release of PAR from the mixed ligand intermediate RCuY is the rate-determining step. The substitution reaction for the copper(II)-PAR complex proceeds in the same mechanism with that for the zinc(II)-PAR complex. The difference in reactivity of these complexes is discussed. Cu-PAR bond is weakened in a distorted octahedron of the intermediate RCuY before the release of PAR.
- 公益社団法人 日本化学会の論文
著者
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Yamada Shinkichi
Laboratory Of Analytical Chemistry Faculty Of Engineering Shizuoka University
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Funahashi Shigenobu
Laboratory Of Analytical Chemistry Department Of Chemistry Faculty Of Science Nagoya University
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Tanaka Motoharu
Laboratory of Analytical Chemistry Faculty of Science Nagoya University
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