Nathan D. Schley
The aim of the Schley research group is the application of organometallic chemistry to unmask latent reactivity in organic substrates. Oxidation of simple hydrocarbons provides functional groups which serve as handles for further transformations, but methods for selective oxidation of C-H bonds are limited. Our goal is to meet the challenge of enabling new oxidative, catalytic transformations of C-H bonds by making use of unconventional activation strategies.
Recent developments in transition metal catalysis have shown that ligands that actively participate in chemical transformations have the potential to have a profound impact on the reactivity of metal ion in catalytic transformations. Broadly speaking, ligand participation can include redox non-innocence, involvement in concerted heterolytic bond formation or cleavage, and the ability to engage in activating, secondary coordination-sphere interactions with the substrate. We aim to introduce a diversity of functional ligands as supporting platforms for catalysis that make use of these and other modes of ligand participation in catalysis. Our long term goal is to capitalize on the ability of functional ligands to define the reactivity of the supported metal ion to develop new non-precious metal catalysts for existing catalytic transformations requiring platinum-group metals.
Some of our research projects include:
- Aerobic oxidation chemistry at late transition metal heterobimetallics – Nature has evolved highly specialized metal-containing enzyme active sites for a variety of challenging transformations. In addition to enzymes containing a single metal ion, bi- and polymetallic active sites are critical to the function of certain enzymes. We can take inspiration from nature through the use of two dissimilar metal ions in a single ligand platform, and exploit the resulting reactivity of bridging ligands and intermediates in catalysis. Our studies in this area will center on the production of reactive late-metal μ-hydroxides under aerobic conditions.
- Net C-H functionalization through pi-arene catalysis – Stoichiometric functionalization chemistry of pi-arene complexes is a well-established class of reactions which remain underutilized by virtue of the lack of catalytic protocols. We aim to develop catalysts that both activate the coordinated arene towards nucleophilic attack and maintain favorable arene exchange kinetics under mild conditions.
- Fischer carbene participation in dehydrogenation chemistry – N-heterocyclic carbene ligands are common σ-donor spectator ligands in transition metal catalysis, while carbene ligands lacking α-heteroatom stabilization function as reactive intermediates in processes including olefin metathesis. We will explore the reversible reactivity of weakly-stabilized Fischer carbene ligands with the goal of demonstrating their ability to function as functional ligands in catalysis.