title: Controlling binding dynamics of corrin-based chemosensors for cyanide.
abstract: This paper describes a strategy to control the binding dynamics between cyanide and aquacyanocorrinoids on the molecular level. Aquacyanocorrinoids represent an important class of chemosensors and convert upon cyanide coordination to the corresponding dicyano derivatives. Structure-reactivity relationships were investigated for the first time by synthesizing and studying three diastereomerically pure aquacyanocorrinoids differing either in the configuration of the axially bound ligands or in the nature of remote side chains located at the periphery of the corrin macrocycle. Substitution of cobalt-coordinated water with cyanide was investigated using stopped-flow measurements between 5 and 30 °C, and second order rate constants and activation parameters were determined. In particular, it is demonstrated that the binding kinetics depend not only on (i) the configuration at the central metal center but also on (ii) the remote structural modifications of the macrocycle.
authors: Department of Chemistry, University of Zürich , Winterthurerstrasse 190, 8057 Zürich, Switzerland.
authors: Balz
authors: B
authors: Aebli
authors: Christine
authors: C
authors: Männel-Croisé
authors: Felix
authors: F
authors: Zelder