Kinetics of ligand substitution reaction of some aminopolyacetatonickel(II) complexes with reference to activation parameters.
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概要
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The substitution reactions of some Ni(II)–L complexes (L: ethylenediamine-<I>N</I>,<I>N</I>′-diacetate, edda<SUP>2−·</SUP>, nitrilo-triacetate, nta<SUP>3−·</SUP>, iminodiacetate, ida<SUP>2−</SUP>) with 4-(2-pyridylazo)resorcinol (H<SUB>2</SUB>par) have been studied spectrophoto-metrically at <I>I</I>=0.10. Rate constant <I>k</I> (mol dm<SUP>−3</SUP>, s) at 25°C, activation enthalpy <I>ΔH</I><SUP>\neweq</SUP>/kJ mol<SUP>−1</SUP> and activation entropy <I>ΔS</I><SUP>\neweq</SUP>/J K<SUP>−1</SUP> mol<SUP>−1</SUP> are respectively: 1.7×10<SUP>3</SUP>, 58.5 and 12.5 for <I>k</I>[Ni<SUP>2+</SUP>][Hpar<SUP>−</SUP>]; 4.0×10<SUP>2</SUP>, 51.8 and −22 for <I>k</I>[Ni(nta)<SUP>−</SUP>][Hpar<SUP>−</SUP>]; 1.0×10<SUP>3</SUP>, 41.8 and −46 for <I>k</I>[(par)Ni(edda)][Hpar<SUP>−</SUP>]; 2.7×10<SUP>−4</SUP>, 109 and 30 for <I>k</I>[(par)Ni(edda)<SUP>2−</SUP>]; 5.1×10<SUP>3</SUP>, 88 and 17 for <I>k</I>[(par)Ni(Hedda)<SUP>−</SUP>]; 1.7×10<SUP>3</SUP>, 122 and 226 for <I>k</I>[Ni(ida)][Hpar<SUP>−</SUP>]. In terms of activation parameters some discussions are made on the effect of coordinated ligands on the lability of leaving ligands and pre-equilibrium involving partial dissociation of leaving ligands.
- 公益社団法人 日本化学会の論文
著者
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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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