• NIH Postdoctoral Fellow, California Institute of Technology, CA, 2012-2015
• PhD, University of California-Irvine, CA, 2012
• BS, Colorado State University, CO, 2007

• Organometallic Chemistry
• Inorganic and Organic Chemistry
• Bioinorganic Chemistry

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. We focus on catalysts that contain the element manganese or iron because they are earth-abundant elements. Our aim is to use these new catalysts to develop practical, sustainable organic methodologies that currently require expensive and toxic elements. Manganese and iron catalysts also have unique chemical properties that sparked our interest and constitute the focus of some of our fundamental studies that will benefit our society through innovative, sustainable chemistry. Reactions we are interested in are atom and energy efficient processes like acceptorless 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:

• organic synthesis (ligand & substrate synthesis, organic product analysis)
• inorganic synthesis (transition metal complex synthesis)
• organometallic chemistry (metal carbonyls, metallocenes, photochemistry)
• catalysis (substrate screening, reaction optimization)
• characterization techniques (electrochemistry, EPR, NMR, FTIR, UV-vis, XRD, MS)
• mechanistic studies (kinetics, substrate monitoring, hypothesis validation)

Organometallic Chemistry – Catalysis

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. We also discovered the first examples of Mn catalyzed allylic alcohol isomerizations and chemoselective chalcone reductions. Currently, we are developing these methodologies and discovering new Mn catalyzed reactions.

Bioinorganic Chemistry – Designing Synthetic Oxygenases

Many oxidations in biology use O₂ from air and occur in proteins called nonheme oxygenases. These proteins have inspired us to prepare new catalysts and develop methodologies that use air, a generously abundant resource, with earth abundant catalysts. However, making a synthetic analog that functions like an enzyme is difficult. Our approach is to design synthetic model complexes that adhere to certain design principles, inspired directly from the natural binding sites. In addition to preparing the new catalysts, we also develop functional synthetic models into sustainable methodologies that use O₂ as the sole oxidant.

• Vigneswaran, V.; MacMillan, S. N.; Lacy,* D. C. Beta-Amino Phosphine Mn Catalysts for 1,4-Transfer Hydrogenation of Chalcones and Allylic Alcohol Isomerization. Organometallics 2019, 38, 4387-4391. DOI: 10.1021/acs.organomet.9b00692
• Kadassery, K. J.; MacMillan, S. N.; Lacy,* D. C. Resurgence of organomanganese(I) chemistry. Bidentate phosphine-phenolate Mn(I) complexes. Inorg. Chem. 2019, 58, 10527-10535. DOI: 10.1021/acs.inorgchem.9b00941
• Lacy,* D. C. Applications of the Marcus cross relation to inner sphere reduction of O₂: implications in small-molecule activation. Inorg. Chem. Front. 2019, 6, 2396-2403. DOI: 10.1039/C9QI00828D
• Kadassery, K. J.; Lacy,* D. C. Pentacarbonylmethylmanganese(I) as a synthon for Mn(I) pincer catalysts. Dalton Trans. 2019, 48, 4467-4470. DOI: 10.1039/C9DT00529C
• Kadassery, K. J.; Sethi, K.; Lacy,* D. C. CO-photolysis-induced H-atom transfer from Mn(I)O–H bonds. Inorg. Chem. 2019, 58, 4679-4685. DOI: 10.1021/acs.inorgchem.9b00322
• Cannella, A. F.; Surendhran,§ R.; MacMillan, S. N.; Gupta, R.; Lacy,* D. C. Electronically varied manganese tris-arylacetamide tripodal complexes. J. Coord. Chem. 2019, 72, 1287-1297. DOI: 10.1080/00958972.2019.1601714
• Crawley, M.; Kadassery, K. J.; Oldacre, A. N.; Freidman, A. E.; Lacy,* D. C.; Cook,* T. R. Rhenium(I) phosphazane complexes for electrocatalytic CO₂ reduction. Organometallics 2019, 38, 1664-1676. DOI: 10.1021/acs.organomet.9b00138
• Kadassery, K. J., MacMillan, S. N.; Lacy,* D. C. Bis-phosphine phenol and phenolate Mn(I) complexes: manganese(I) catalyzed Tishchenko reaction. Dalton Trans. 2018, 47, 12652-12655. DOI: 10.1039/C8DT02933D
• Guan, Y.-S.; Zhong, G.; Hu, Y.; Cannella, A. F.; Li, C.; Lee, N.; Jia,* Q.; Lacy,* D. C.; Ren,* S. Magnetoelectric radical hydrocarbons. Adv. Mater. 2018, 31, 1806263. DOI: 10.1002/adma.201806263
• Surendhran, R.;^‡ D’Arpino, A. A.; ^‡ Bao, Y. S.;^‡ Cannella, A. F.; MacMillan, S. N.; Lacy,* D. C. Deciphering the Mechanism of O₂ Reduction with Electronically Tunable Non-Heme Iron Enzyme Model Complexes Accepted Chem. Sci. 2018, DOI: 10.1039/C8SC01621F
• Cannella, A. F.; Dey, S. K.; MacMillan, S. M.; Lacy,* D. C. Structural Diversity in Pyridine and Polypyridine Adducts of Ring Slipped Manganocene: Correlating Ligand Steric Bulk with a Quantified Non-Ideal Hapticity Parameter. Dalton Trans. 2018, 47, 5171 – 5180. Cover article.
  
• Kadassery, K. J.; Dey, S. K.; Cannella, A. F.; Surendhran,^§ R.; Lacy,* D. C. Photochemical Water-Splitting with Organomanganese Complexes. Inorg. Chem. (2017), 56, 9954–9965. DOI: 10.1021/acs.inorgchem.7b01483
  
• Kadassery, K. J.; Dey, S. K.; Friedman, A. E.; Lacy,* D. C. Exploring the Role of Carbonate in the Formation of an Organomanganese Tetramer. Inorg. Chem. (2017), 56, 8748-8751. DOI: 10.1021/acs.inorgchem.7b01438
  

§ Undergraduate authors; * corresponding authors