Redox active Azothioformamide (ATF) ligands can dissolve and/or coordinate various transition metal and metal salts to form unique ligand:metal coordination complexes. Single crystal X-ray diffraction and UV-Vis titration studies have indicated that ATF ligands form 1:1 µ-X halogen-bridged dimers from copper(I) halides, and 2:1 ligand:metal complexes from Copper(I) salts containing non-coordinative counterions (BF4-, PF6-). When ATFs are appended with electron-donating moieties there is an increased binding association which was confirmed by DFT calculations to show more exergonic interactions while electron-withdrawing moieties provided weaker binding association interactions. Coordination studies and crystallographic structure identification are now guiding complex choices in catalyst selection and future catalyst design. For example, ATFs with added electron donating groups, when complexed with CuII were found to be excellent catalysts to produce propiolic acids from terminal alkynes through reductive insertion of CO2. A variety of aryl and alkyl substrates were evaluated giving yields from 23% - 99%. ATF CuI catalysts have also yielded favorable results in CuAAC “Click” reactions. Reaction scope, limitations, proposed mechanisms, and reaction conditions will be discussed.

Evaluating coordinative binding and catalysis of redox active azothioformamide metal systems

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