Advances in non-linear computational tools have allowed for better evaluation of binding models and associated constants with the ability to add in statistical variability, perform global parameter fitting, and simultaneously converge on an optimal solution set. However, estimating these constants can remain challenging, especially in weakly binding systems with relatively fast exchange rates. Herein, we present recent advances in higher order binding constant determination and computational coupling of UV-Vis and NMR measurements to evaluate binding models and association constants of various copper species with redox active arylazothioformamide ligands. Arylazothioformamide ligands  and copper halide species, copper(I) bromide and copper(I) iodide, are predicted to form 1:1 metal:ligand coordination complexes, while tetrakis(acetonitrile)copper(I) tetrafluoroborate and tetrakis(acetonitrile)copper(I) hexafluorophosphate and predicted to form 1:2 coordination complexes in acetonitrile. The coupling of NMR and UV-Vis techniques allows for simultaneous determination of association constants using two independent techniques which typically operate under different concentration regimes, increasing confidence in the resultant fit.

Obstacles in 1:2 metal-ligand coordination complexes: Approaches to navigating the degree of freedom landscape

256th National Meeting (2018)

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