Synthesis of iron, manganese, and ruthenium coordination complexes toward sustainable chemistry; organometallic chemistry; synthetic oxygenases; electrochemical, photochemical, and chemical small molecule activation studies; bio-inspired catalyst design
657 Natural Sciences Complex
Buffalo NY, 14260
Phone: (716) 645-4114
Fax: (716) 645-6963
Here at the University at Buffalo, we design new synthetic catalysts for environmentally friendly (green) chemical transformations. For those who don’t know, catalysts are like enzymes – they facilitate chemical reactions that otherwise will not occur on meaningful timescales or efficiencies. Our studies are focused on iron- and manganese-based catalysts because they are earth-abundant elements, but we also study Ru-based systems. Our aim is to replace expensive and toxic catalysts that are currently in use and to develop practical, sustainable organic methodologies. Additionally, Mn and Fe also have unique chemical properties that sparked our interest and constitute the focus of some of our fundamental studies. The idea is that by gaining fundamental knowledge about Mn and Fe, we make progress toward improving our society through innovative, sustainable chemistry. Reactions we are interested in are atom and energy efficient processes like hydrogenations, esterifications, aerobic oxidations, and water splitting.
To accomplish these goals, students who join the Lacy Lab will participate in activities that include the following:
Organometallic Chemistry – Catalysis
A primary effort in the Lacy research program is the synthesis of new earth-abundant Mn(I) catalysts for green acceptorless chemical transformations. These include (de)hydrogenation reactions and esterification through disproportionation of aldehyde substrates (i.e. Tishchenko reaction). The discovery that Mn(I) complexes can catalyze hydrogenative transformations occurred just one year after the Lacy group was established. Most of these studies used ligands designed for Ru. As a consequence, a major deficiency in the area is a lack of ligands specifically tailored to Mn. Therefore, we prepare new ligands, study their coordination chemistry with Mn, and probe their efficiency in catalytic hydrogenations or dehydrogenations. Following this strategy, we were the first discover that Mn can catalyze the Tishchenko reaction and are furthering this chemistry to prepare unsymmetrical esters.
Bioinorganic Chemistry – Designing synthetic oxygenases
Many processes in biology involve the oxidation of organic molecules at iron and manganese enzyme active sites. Such processes often require molecular oxygen (O2) and serve as inspiration for new methods of using this generously abundant resource to perform synthetic oxidations with earth abundant catalysts. The enzymes that carry out these types of reactions have specific, yet diverse coordination environments. Making a synthetic analog that functions as a catalyst is difficult. Our approach is to design synthetic model complexes that adhere to certain design principles. We also are developing the few small known examples of functional synthetic models to practical organic synthesis since O2 is such an abundant resource and therein sustainable methodologies.
§ Undergraduate authors; * corresponding authors