Nicholas Piro joined the Albright community in 2016 and has taught across the chemistry
curriculum including introductory general chemistry, inorganic chemistry, and advanced topics
courses. His research interests are in synthetic inorganic chemistry and the design of molecules
with transition metal ions at their core. In collaboration with undergraduates at Albright
College, Dr. Piro is studying the coordination chemistry of guanidine based ligands with first-
row transition metals, e.g. iron, cobalt and copper, and the ability of these complexes to
catalyze difficult reactions of organic molecules. He is also interested in the design of bimetallic
complexes to carry out important transformations of small molecules, such as the reduction of
carbon dioxide to useful products.

Dr. Piro earned his PhD in Inorganic Chemistry from the Massachusetts Institute of
Technology, and followed up his training with a three year Miller Fellowship at the University of
California, Berkeley. He then moved to Pennsylvania to research f-block chemistry at the
University of Pennsylvania. Immediately prior to arriving at Albright College, Dr. Piro taught for
three years at Villanova University, where he also managed the Small-Molecule X-ray
Diffraction Lab.

Synthetic Chemistry

Dr. Piro is a synthetic inorganic chemist. He enjoys designing and synthesizing new molecules
with metal ions at their core and exploring the reactivity of these new molecules. Many of
these molecules are sensitive to air and/or water and so synthesis and characterization of the
complexes must be carried out under air-free conditions.

X-ray Crystallography

Dr. Piro also has a passion for X-ray crystallography, a technique he uses to characterize the
structure of molecules in the solid state. Through an ongoing collaboration with Villanova
University, Dr. Piro routinely uses this technique to determine the structure of new molecules
synthesized in his lab, providing a detailed snapshot of what these molecules look like.

Catalysis with Guanidine Complexes of First-row Transition Metal Ions

The ability to introduce new functionality to organic molecules is incredibly important for commodity, fine chemical, and pharmaceutical synthesis. The organic chemist’s toolbox is full of methods to interconvert between existing functional groups, but the ability to introduce new chemical handles in place of hydrocarbon bonds remains underdeveloped.

The Piro Lab is working to develop catalysts that utilize cheap and abundant metal ions, such as iron, copper, and cobalt, to carry out some of these difficult reactions in a “greener” and more efficient manner.  Their approach uses a family of custom designed molecular supports, known as ligands, to control and direct the reactivity of the metal ions. The particular ligands being used in the Piro Lab are nitrogen-rich guanidine ligands that are designed to be stable to the reaction conditions that might otherwise decompose the catalysts. Dr. Piro is also deeply interested in studying the fundamental relationships between structure, bonding, and reactivity that these complexes display.

Bimetallic Complexes with Dissimilar Coordination Environments

Transforming small molecules–such as CO₂, N₂, N₂O, and CH­₄– into useful or more benign products is often hindered by either slow reaction rates or lack control over products. However, nature carries out a great number of these transformations rapidly and selectively at mild temperatures. A look at the natural enzymes that perform these transformations reveals certain characteristics. One repeated theme is the use of bimetallic active sites that have differences in either the identity of the metals or the molecules surrounding the metal ions.

The Piro Lab is designing molecules that incorporate two metals which can act in concert to either localize and activate substrates for reactivity, or to polarize bonds through cooperative acid-base behavior. This will allow for the exploration of a wide variety of small molecule activations and transformations. Particular long-term goals of this project are to study reactions involving CO₂ and nitrogen oxides and their transformation to useful products.

• CHE105: General Analytical Chemistry I and lab
• CHE207: Organic Chemistry I (laboratory)
• CHE208: Organic Chemistry II (laboratory)
• CHE324: Inorganic Chemistry and lab
• CHE412: Advanced Topics in Chemistry

M. V. Savakinas, O. M. Frey, N. A. Piro, I. J. Rhile; C. S. Hamann. “Expanding the Scope of an Electrophilic Aro- matic Substitution Discovery Experiment Including Hydride and Methyl Shifts.” J. Chem. Ed. 2021, 98, 3999-4008. DOI:10.1021/acs.jchemed.1c00558

L. M. Thierer, S. E. Jenny, V. Shastri, S. E. Jenny, M. R. Donley, L. M. Round, N. A. Piro, W. S. Kassel, C. L. Brown, T. J. Dudley, D. L. Zubris. “Amino Pyridine Iron(II) Complexes: Characterization and Catalytic Application for Atom Transfer Radical Polymerization and Catalytic Chain Transfer.” J. Organomet. Chem. 2020, 924, 121456. DOI:10.1016/j.jorganchem.2020.121456

Z. M. Gehman, W. S. Kassel, N. A. Piro. “1:1 Co-crystal of 3-ethyl-4-methyl-3-pyrrolin-2-one and 3-ethyl-4-methyl-3-pyrrolin-2,5-dione.” IUCrData 2019, 4, x191209. DOI:10.1107/S2414314619012094.

J. E. Allen, W. S. Kassel, N. A. Piro. “Synthesis, Structures and Characterization of Complexes Containing a 2,6-Bis(guanidinyl)pyridine Ligand on Iron(II), Cobalt(II), Nickel(II), Copper(I), Copper(II) and Zinc(II).” Polyhedron 2018, DOI: 10.1016/j.poly.2018.08.012

H. H. Wilson, C. A. Koellner, Z. M. Hannan, C. B. Endy, M. W. Bezpalko, N. A. Piro, W. S. Kassel, M. D. Sonntag, C. R. Graves. “Synthesis and Characterization of Neutral Ligand a-Diimine Complexes of Aluminum with Tunable Redox Energetics.” Inorg. Chem. 2018, 57, 9622-9633. DOI:10.1021/acs.inorgchem.8b00045.

N. A. Piro, J. R. Robinson, P. J. Walsh, E. J. Schelter. “The Electrochemical Behavior of Cerium(III/IV) Complexes: Thermodynamics, Kinetics and Applications in Synthesis.” Coord. Chem. Rev. 2014, 260, 21-36.

N. A. Piro, M. F. Lichterman, W. H. Harman, C. J. Chang. “A Structurally Characterized Nitrous Oxide Complex of Vanadium.” J. Am. Chem. Soc. 2011, 133, 2108-2111.

N. A. Piro, J. S. Figueroa, J. T. McKellar, C. C. Cummins. “Triple-Bond Reactivity of Diphosphorus Molecules.” Science 2006, 313, 1276–1279.

Henry P. and M. Paige Laughlin Annual Distinguished Faculty Award for Scholarship, 2019

Pittsburgh Conference Memorial National College Grant, 2019

American Chemical Society Petroleum Research Foundation Grant, 2017