Monday, May 14, 2012
Correlation of Electronic Structure to Reactivity in Organometallic Catalysis and Polynuclear Small Molecule Activation
Theodore Betley, Assistant Professor of Chemistry and Chemical Biology, Department of Chemistry and Chemical Biology, Harvard University
Abstract: Electronic structure considerations dictate the stability and/or reactivity of both mono- and polynuclear complexes. The utilization of weak-field ligands have enabled (1) the development of reactive iron-based reagents to catalyze C-H bond functionalization, and (2) directly control M-M interactions in polynuclear clusters to unveil a host of new physical properties. In the latter context, the close proximity of the metal ions within the polynuclear architectures enforce direct metal-orbital overlap, giving rise to fully delocalized electronic configurations. Within this delocalized framework, ligand alterations allows for tuning of the resultant electronic structure from low-spin to high-spin configurations. Within both bodies of chemistry, obtaining high-spin electronic configurations are necessary to achieve catalysis or small molecule activation.