• 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. 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:

• 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

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.

• 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