Inorganic Chemistry, Theoretical Chemistry Research Projects Much of the emphasis in our research group involves the application of accurate quantum chemical methods to the analysis of large molecular systems. A brief summary of each of these projects is given below. Homogeneous organometallic systems have recently been successful in modeling several key steps of the heterogeneous desulfurization reaction, and our group has applied high-level computational methods to provide additional details regarding the bond scission reaction mechanism, the relative energetics of the various substrate binding modes and the intramolecular rearrangement pathways.
Work is in progress on mechanistic aspects of the denitrogenation reaction.
Significant debate has focused on the role played by pi-backbonding to the axially coordinated ligands. To this end, our group is engaged in a collaborative effort with the research group of Dr. Cassandra Eagle of Appalachian State University to synthesize and study a variety of new axially ligated rhodium carboxylates. Led by Dr. Toby Allen, a research team at ECU has recently derivatized aromatic porphyrinoid polypyrrole macrocycles through a substitution of the pyrrole rings by imidazole groups. Unique to this molecule is the arrangement of nitrogen donor atoms not only within the binding pocket but also external to the macrocycle, creating the opportunity for exocyclic metal ion binding and the possible formation of molecular wires with unique magnetic properties. Our collaboration with this group has resulted in accurate calculations which have assisted in the 13C and 1H NMR spectroscopic characterization of these compounds and have provided an explanation of the unusual stability of the non-aromatic reduced form of the compound.