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Controlling binding dynamics of corrin-based chemosensors for cyanide


Aebli, Balz; Männel-Croisé, Christine; Zelder, Felix (2014). Controlling binding dynamics of corrin-based chemosensors for cyanide. Inorganic Chemistry, 53(5):2516-2520.

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.

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.

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6 citations in Web of Science®
6 citations in Scopus®
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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2014
Deposited On:20 Feb 2015 10:15
Last Modified:05 Apr 2016 18:56
Publisher:American Chemical Society
ISSN:0020-1669
Publisher DOI:https://doi.org/10.1021/ic4026427

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