Copper phenanthroline complexes have been widely studied for many reasons, such as their use as reagents in molecular biology, and interesting photophysical behavior.  Typically, the bis-phenanthroline complexes exhibit a five-coordinate geometry for the cupric complexes, with one donor being derived from solvent or counterion. Conversely, the cuprous state is invariably observed to have a four-coordinated geometry. Cupric complexes bearing substituents at the 2- and 9-positions of the ligands, which impose steric congestion close to the copper centers, have long beenknown to show facilitated reduction to afford the less congested cuprous forms. More recent studies of complexes of this type, however, have shown that the steric strain can also be alleviated by loss of the solvent ligand from the cupric centers, affording four-coordinate Cu(II) complexes.  We will report on the influence of various proximal substituents in determining the extent of formation of the four-coordinate cupric complexes both in solution and in the solid state, and the competition between the desolvation and reduction processes.

Solvation equilibria of proximally-substituted copper bis-phenanthroline derivatives

241st National Meeting (2011)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.