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Formation and Dissociation Mechanism of Amide Complexes, IV. Protonation and deprotonation of the Cu2+ and Ni2+ complexes of 3,7-diazanonanediamide and 3,7-diazanonane-N,N′-diethylamide

✍ Scribed by Andreas D. Zuberbühler; Thomas A. Kaden

Publisher
John Wiley and Sons
Year
1974
Tongue
German
Weight
365 KB
Volume
57
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

The protonation and deprotonation rates of the coordinated amide groups in the Ni^2+^ and Cu^2+^ complexes of 3,7‐diazanonanediamide (DANA) and in the Cu^2+^ complex of 3,7‐diazanonane‐N,N′‐diethylamide (DANEA) have been studied by stopped‐flow techniques. For the interconversion M(H~−2~L) ⇌ ML, two consecutive reactions are observed in the case of Cu^2+^ with DANA or DANEA, whereas there is only one reaction for Ni^2+^ with DANA. Cu(H~−2~DANEA) is unusually labile, indicating a strong interaction between the N‐ethyl groups. The conversion of the O‐ into the N‐coordinated amide groups in NiDANA^2+^ is 25 times slower than in CuDANA^2+^. In the case of Ni^2+^ this excludes a step with water substitution, which is involved in one of the reaction paths observed for the Cu^2+^ complexes, since the rates of water exchange differ by a factor of 10^5^ for the two metal ions.

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