Kinetics of ternary complex formation with the (nitrilotriacetato)copper(II) complex

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Abstract

Ligand substitution reactions of the (nitrilotriacetato)copper(II) complex (CuNTA-) with simple mono- and bidentate ligands (L) have been investigated by making use of the temperature-jump relaxation technique. At 25°C, the forward rate constants for reaction CuNTA- + L = CuNTA(L)- are as follows: L = NH3, 1.5 × 108 M-1 s-1; L = CH3NH2, 3.4 × 107 M-1 s-1; L = glycinate, 1.1 × 108 M-1 s-1; L = α-alaninate, 4.9 × 107 M-1 s-1; L = β-alaninate, 3.8 × 107 M-1 s-1; L = 2,2′-bipyridine, 1.2 × 106 M-1 s-1; L = 1,10-phenanthroline, 2.2 × 105 M-1 s-1. The rate constants for the reactions of the zwitterion form of glycine and α-alanine, CuNTA- + HL± = CuNTA(L)2- + H+, are 1.6 × 103 M-1 s-1 and 1.8 × 103 M-1 s-1, respectively. It was concluded that the reactions of the aliphatic ligands proceed through a dissociative interchange mechanism in which the axial coordination of the entering ligand is the rate-determining step. The unusually slow reactions with the aromatic ligands have been interpreted in terms of steric interference between the coordinated and entering ligandis.

Original languageEnglish
Pages (from-to)1184-1190
Number of pages7
JournalInorganic Chemistry
Volume32
Issue number7
Publication statusPublished - 1993

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Copper
Ligands
copper
ligands
Kinetics
kinetics
Rate constants
zwitterions
Interchanges
alanine
glycine
Alanine
Glycine
Substitution reactions
substitutes
interference
Temperature
temperature

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Kinetics of ternary complex formation with the (nitrilotriacetato)copper(II) complex. / Fábián, I.

In: Inorganic Chemistry, Vol. 32, No. 7, 1993, p. 1184-1190.

Research output: Contribution to journalArticle

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N2 - Ligand substitution reactions of the (nitrilotriacetato)copper(II) complex (CuNTA-) with simple mono- and bidentate ligands (L) have been investigated by making use of the temperature-jump relaxation technique. At 25°C, the forward rate constants for reaction CuNTA- + L = CuNTA(L)- are as follows: L = NH3, 1.5 × 108 M-1 s-1; L = CH3NH2, 3.4 × 107 M-1 s-1; L = glycinate, 1.1 × 108 M-1 s-1; L = α-alaninate, 4.9 × 107 M-1 s-1; L = β-alaninate, 3.8 × 107 M-1 s-1; L = 2,2′-bipyridine, 1.2 × 106 M-1 s-1; L = 1,10-phenanthroline, 2.2 × 105 M-1 s-1. The rate constants for the reactions of the zwitterion form of glycine and α-alanine, CuNTA- + HL± = CuNTA(L)2- + H+, are 1.6 × 103 M-1 s-1 and 1.8 × 103 M-1 s-1, respectively. It was concluded that the reactions of the aliphatic ligands proceed through a dissociative interchange mechanism in which the axial coordination of the entering ligand is the rate-determining step. The unusually slow reactions with the aromatic ligands have been interpreted in terms of steric interference between the coordinated and entering ligandis.

AB - Ligand substitution reactions of the (nitrilotriacetato)copper(II) complex (CuNTA-) with simple mono- and bidentate ligands (L) have been investigated by making use of the temperature-jump relaxation technique. At 25°C, the forward rate constants for reaction CuNTA- + L = CuNTA(L)- are as follows: L = NH3, 1.5 × 108 M-1 s-1; L = CH3NH2, 3.4 × 107 M-1 s-1; L = glycinate, 1.1 × 108 M-1 s-1; L = α-alaninate, 4.9 × 107 M-1 s-1; L = β-alaninate, 3.8 × 107 M-1 s-1; L = 2,2′-bipyridine, 1.2 × 106 M-1 s-1; L = 1,10-phenanthroline, 2.2 × 105 M-1 s-1. The rate constants for the reactions of the zwitterion form of glycine and α-alanine, CuNTA- + HL± = CuNTA(L)2- + H+, are 1.6 × 103 M-1 s-1 and 1.8 × 103 M-1 s-1, respectively. It was concluded that the reactions of the aliphatic ligands proceed through a dissociative interchange mechanism in which the axial coordination of the entering ligand is the rate-determining step. The unusually slow reactions with the aromatic ligands have been interpreted in terms of steric interference between the coordinated and entering ligandis.

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