Cross reactions between nickel(III) peptides and nickel(II) peptides in aqueous solution are used to evaluate the self-exchange rate constants, fcu, of these species. The values of ku for 16 different peptide complexes vary with their structure but can be classified into the following groups: triply deprotonated peptides (1.2 X 105 M'1 s'1), except for H_3G5 (4.2 X 104 M"1 s'1), and doubly deprotonated peptides (1.3 x 104 M'1 s'1). The cross reactions are catalyzed by bridging ligands 5 X 10'3 M Br". The order of enhanced reactivity is Br*
Kreuzungsreaktionen zwischen Ni(III)‐ und Ni(II)‐Komplexen 16 verschiedener Peptide in wäßriger Lösung werden benutzt, um ihre strukturabhän‐ gigen Elektronen‐Selbstaustausch‐Geschwindigkeitskonstanten zu berechnen.
DieStabilitätskonstanten für die axiale Koordination eines einzähnigen Stickstoffliganden (Imidazol, 1‐Methyl‐ und 2‐Methylimidazol, Pyridin, 4‐Methylpyridin, NH3, Azid) an Ni(III)‐Komplexe von Triglycinamid, Tri‐oz‐aminoisobuttersäure und Di‐aaminoisobutyryl‐a‐aminoisobutyramid werden bei 25°C mit Hilfe einer elektrochemischen Methode bestimmt.
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