Redox-active ligands contain multiple low energy transitions that alter the strength of coordination. These ligands display weak-binding coordination when reacted with transition metal salts, as determined through titration experiments, and are excellent substrates for the development of non-linear models for binding constant determination. One intriguing redox-active ligand series, the arylazothioformamide (ATF) 1has a rather straightforward synthesis that lends itself to steric and electronic diversity. We have begun the creation of a small library of ATF chelating ligands with varied electronic components and initiated titration-based coordination studies using various transition metal salts. Change in affinity, selectivity, and coordination have been seen in these derivatives as in 2, 3, and 4 all possessing ATF ligands in neutral form while reaction with zerovalent transition metals, such as copper results in singly reduced ligands, shown in complex 5. Further, electron withdrawing and electron donating derivatives have been assessed through experimental (UV-Vis and NMR titrations, electrochemistry) but alsothrough computational means (computational modeling of X-ray crystal structures, and advanced equilibrium models) yielding a hybrid model. This presentation will discuss how the synthetic efforts in combination with the hybrid assessment model interplay to obtain reliable association constants consistently in simple (1:1) and complex (2:1) binding systems. This talk will highlight the synthetic aspects and experimental protocols towards building a better understanding of binding in redox-active ligand systems.

Building a better understanding of binding in redox-active arylazothioformamide ligand systems

2019 Fall National Meeting

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