Modulating the Primary and Secondary Coordination Spheres within a Series of CoII-OH Complexes.

The interplay between the primary and secondary coordination spheres is crucial to determining the properties of transition metal complexes. To examine these effects, a series of trigonal bipyramidal Co-OH complexes have been prepared with tripodal ligands that control both coordination spheres. The ligands contain a combination of either urea or sulfonamide groups that control the primary coordination sphere through anionic donors in the trigonal plane and the secondary coordination sphere through intramolecular hydrogen bonds. Variations in the anion donor strengths were evaluated using electronic absorbance spectroscopy and a qualitative ligand field analysis to find that deprotonated urea donors are stronger field ligands than deprotonated sulfonamides. Structural variations were found in the CoII-O bond lengths that range from 1.953(4) to 2.051(3) Å; this range in bond lengths were attributed to the differences in the intramolecular hydrogen bonds that surround the hydroxido ligand. A similar trend was observed between the hydrogen bonding networks and the vibrations of the O-H bonds. Attempts to isolate the corresponding CoIII-OH complexes were hampered by their instability at room temperature.