Research
Research in The Tilley Group involves exploratory synthetic, structural, and reactivity studies on novel inorganic and organometallic systems. Reactivity studies focus on compounds that exhibit unusual electronic and/or coordination environments for the metal center, and discovery of new chemical transformations. Reactivity studies are guided by mechanistic investigations that shed light on how reactions proceed. Metal-mediated routes to new polymers are being explored, and molecular, chemical approaches to the designed construction of advanced solid state materials and heterogeneous catalysts are being developed.
Organometallic Chemistry and Homogeneous Catalysis:
Research in organometallic chemistry involves the synthesis of transition metal complexes that exhibit novel chemical properties, often via the design and introduction of new ancillary ligands that control the first- and second-coordination spheres of a metal center. There is also particular interest in exploring metal centers in unusual electronic environments and oxidation states.
Reactivity and Catalysis with Two-Coordinate Metal Complexes
Electrophilic Metal Complexes in Bond Activations and Catalysis
Transition Metal-Main Group Chemistry:
A long-standing interest of the group concerns identification of novel bonding and reactivity modes for reactive main-group element fragments within the coordination sphere of a metal. These studies then lead the way to development of new catalytic cycles for synthesis of organoelement compounds.
Organic Materials from New Metal-Mediated Methods:
This program targets new electronic materials via the development of new metal-mediated synthetic routes. The initial focus was on development of metal-catalyzed dehydrocoupling routes to σ-conjugated main group polymers (e.g., polysilanes and polystannanes). Subsequently, the program was expanded to include use of zirconocene-coupling of alkynes for the synthesis of π-conjugated oligomers and polymers, mechanistic studies on these couplings, and the use of reversible couplings to prepare macrocycles of variable shapes and sizes. A current effort, which is funded by the National Science Foundation (CHE-1708210), concerns the development of a general, metal-mediated [2+2+n] cycloaddition route to large polycyclic aromatic hydrocarbons (PAHs) and related carbon nanostructures.
Catalysis in Energy Conversion Chemistry:
Efforts in the group focus on development of efficient routes to renewable chemical fuels from solar energy. Primary objectives include identification of inexpensive, efficient catalysts that drive energetically uphill reactions in the conversion of stable feedstocks (e.g., water and CO2) to potential fuels (e.g., hydrogen and hydrocarbons). Current research is directed toward identification of soluble and surface-bound catalysts for water oxidation and proton reduction. These activities involve the synthesis and evaluations of molecular and nanostructured electrocatalysts. Work with appropriate molecular model systems addresses important mechanistic issues.
Molecular Precursor Routes to Solid-State Materials and Heterogeneous Catalysts:
A project on the molecular design and synthesis of solid-state materials is based on development of chemical routes to complex, 3-dimensional networks via molecular-level control. Primary targets are multi-component, oxygen-containing materials that are fabricated from tailored, oxygen-rich precursor molecules. This approach has been used to obtain new catalysts for selective hydrocarbon oxidations. Related molecular precursors are used to introduce isolated catalytic sites onto the surface of an oxide support. Advantages to the latter method include the increased potential for molecular-level control over structure, the generation of site-isolated catalytic centers, and the availability of good spectroscopic models for the catalytic site. Further efforts employ chemical modifications of the catalyst support surface to enhance binding and activation of substrates, and release of products.