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The configurational stability of metallated cyclam increased with the substitution at nitrogen atoms and isomerism processes of copper(II) complexes have only been observed in the case of partially N-substituted cyclam derivatives: (a) E.K. Barefield, K.A. Foster, G.M. Freeman, K.D. Hodges, Inorg. Chem. 25 (1986) 4663; (b) J. Kotek, P. Lubal, P. Hermann, I. Cisarova, I. Lukes, T. Godula, I. Svobodova, P. Taborsky, J. Havel, Chem. Eur. J. 9 (2003) 233; (c) C. Bucher, J.-C. Moutet, J. Pécaut, G. Royal, E. Saint-Aman, F. Thomas, S. Torelli, M. Ungureanu, Inorg. Chem., in press.
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The configurational stability of metallated cyclam increased with the substitution at nitrogen atoms and isomerism processes of copper(II) complexes have only been observed in the case of partially N-substituted cyclam derivatives: (a) E.K. Barefield, K.A. Foster, G.M. Freeman, K.D. Hodges, Inorg. Chem. 25 (1986) 4663; (b) J. Kotek, P. Lubal, P. Hermann, I. Cisarova, I. Lukes, T. Godula, I. Svobodova, P. Taborsky, J. Havel, Chem. Eur. J. 9 (2003) 233; (c) C. Bucher, J.-C. Moutet, J. Pécaut, G. Royal, E. Saint-Aman, F. Thomas, S. Torelli, M. Ungureanu, Inorg. Chem., in press.
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The characteristic time of a votammetry experiment is τ=RT/Fv; it corresponds to the time needed, at the given potential scan rate v, to achieve a 25 mV run of the potential. The half life time θ of the electrogenerated species can be roughly estimated from the amount of chemical reversibility of the wave: θ is close to the τ value associated with the lower scan rate at which the wave exhibits a distinct although small amount of reversibility; another way to estimate θ is to identify it with 10τ′ where τ′ is now associated with the scan rate v′ for which the wave is approximately 50% reversible. Obviously, these two empiric methods only provide orders of magnitude for θ or the pseudo first order rate constant k≈1/θ.
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