Synthesis, Charactertization and Properties of Polyimidazole Compounds

When I started my career as an Assistant Professor in the Department of Chemistry at the University of Louisville, my research focused on the synthesis, characterization and reactivity of biologically relevant imidazole compounds. Prior to the beginning of my work, there were only a few examples of imidazole containing compounds.  My group developed new synthetic procedures to make polyimidazole ligands and studied their coordination chemistry and electronic and physical properties. Over the years, we studied complexes containing metals, such as, Fe, Mn, Zn and Cu, which served as models of enzyme active sites. In collaboration with Professor D.N. Hendrickson, we were able to replicate key spectroscopic and electronic properties of non-heme iron enzymes, such as hemerythrin and purple acid phosphatase, as well as urease. Later in collaboration with Dr. R. H. Fish we developed functional biomimetics of the non- heme iron protein methane monooxygenase that efficiently catalyzed the oxidation of alkane C—H bonds. Finally, my group prepared and characterized a series of polyimidazole compounds containing pendent amide groups that facilitate second coordination effects. One of these copper complexes bonds and stabilizes a hydroperoxide ligand. . Representative and informative articles on our studies are listed below.

Citations

R. M. Buchanan, M. S. Mashuta,  J. F. Richardson, Q. Li, D. N. Hendrickson, "Active Site Model of Urease.  Synthesis, Structure, and Properties of a Binuclear Ni(II) Complex Containing a Polyimidazole Ligand", J. Am. Chem. Soc., 1989, 111(12), 4497-4498. doi: 10.1021/ja00194a054.

 

M. S. Mashuta, R. J. Webb, K. J. Oberhausen, J. K. McCusker, J. F. Richardson, R. M. Buchanan, D. N. Hendrickson, "Electron Transfer in FeIIFeIII Model Complexes of Iron-Oxo Proteins", J. Am. Chem. Soc., 1992, 114(10), 3815-3827. doi: 10.1021/ja00036a053. 

 

Rabion, A, Chen, S, Wang, J, Buchanan, RM, Series, J-L, Fish, RH "Biomimetic Oxidation Studies.  9.  Mechanistic Aspects of the Oxidation of Alcohols with Functional, Active Site Methane Monooxygenase Enzyme Models in Aqueous Solutions, J. Am. Chem. Soc., 1995, 117(49), 12356-12357. doi: 10.1021/ja00154a047.

 

L. E. Cheruzel, J. Cui, M. S. Mashuta,  C. A. Grapperhaus, R. M. Buchanan, “N-(2-formyl-1-methylimidazol-4-yl)-2,2-dimethylpropanamide: A versatile reagent for preparing imidazole-amine ligands with variable second-coordination spheres,” Tetrahedron Letters 2011, 52, 4771-4774. doi: 10.1016/j.tetlet.2011.07.025.