Formation kinetics of pendant arm polyamine macrocycles with copper(II)

摘要: The complexation reaction between Cu(II) and a series of cyclam analogue macrocycles with dangling primary amine groups was investigated in aqueous solution. pH dependence the measured 0 5.5 covering range different protonation stages ligands. kinetics observed by stopped-flow measurements followed at many wavelengths. An initial second order results an intermediate which isomerises to stable complex. rate constants for step varied 1.5 × 10−2 M−1 s−1 6.3 × 105 5.3; secondary rates 2 × 10−4 1 24 5.3. successfully analysed terms reactivities differently protonated ligands first complexes step. Ligands unprotonated amines react 106–107 s−1, drop dramatically upon arms ca. 10–102 are very similar parent ligand equivalent protonation. isomerisation is explained ways: protonated, inhibit completely.