Substiutents at the proximal positions of phenanthroline ligands have a profound impact on the behavior of bound copper ions.  Early work showed that such substituents promoted reduction chemistry, which resulted in a lower coordination number and diminished steric stress; our more recent work has shown that ligand loss to form four-coordinate cuprous complexes is a common mode of relief of such steric stress within the cuprous complexes of the ligands, and such effects are quantifiable through titrations that assess the equilibria between the four- and five- coordinate species.  In addition, reduction of the complexes by water appears to be an unexpected but very interesting facet of the their behavior, which will be discussed.

Proximal substituent effects in the coordination equilibria of Cu(II) phenanthroline complexes

243rd National Meeting (2012)

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