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Metal Complexes with Macrocyclic Ligands. XIV. Formation, dissociation and metal exchange with an N2S2-macrocycle

✍ Scribed by Chariklia S. Kallianou; Thomas A. Kaden

Publisher
John Wiley and Sons
Year
1979
Tongue
German
Weight
386 KB
Volume
62
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

10, 10, 12‐Trimethyl‐3,4‐benzo‐1,6‐dithia‐9,13‐diazacyclopentadecen‐dihydrochloride (LH, 2) and its Ni^2+^ complex were synthesized and their reactivity studied. The formation kinetics of 2 with Cu^2+^ were found to be a second order reaction between Cu^2+^ or CuACO^+^ and the monoprotonated form of the ligand LH^+^. The rate constant k = 29 M^−1^S^−1^ is 10^5^–10^6^ times smaller than those of monoprotonated tetraazamacrocycles either because of second bond formation or because of a strong electrostatic interaction between the positive charges of the Cu^2+^ and the ammonium group. The metal‐metal exchange between NiL^+^ and Cu^2+^ was also investigated. The reaction is independent of [Cu^2+^] and has the same rate and activation parameters as the dissociation of NiL^2+^. In contrast to open chain ligands, no mixed complex CuNiL^4+^ as intermediate was observed.

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