Agapie Group Inorganic, Organometallic, and Bioinorganic Chemistry
Synthesis, Mechanism and Catalysis

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Our research will focus on developing molecular solutions to problems related to energy, materials, and health. Having nature as a source of inspiration, we will develop and study systems displaying interactions between multiple molecular centers (metals, Lewis acids, hydrogen bonding functionalities, etc.) to facilitate a variety of chemical processes.

From a small molecule perspective, we will target systems able to perform transformations important in organic methodology, new materials generation as well as in the context of the energy economy. Areas of interest include selective C-H bond functionalization, polymerization of polar monomers, and multielectron processes such as water oxidation to dioxygen and dinitrogen fixation. To attain these goals we will design and synthesize ligand frameworks that allow for the binding of several metals in close proximity. Hydrogen bonding networks and pendant Lewis acids will be built in if believed to be important for the desired transformations. The synthesized multimetallic complexes will be studied using a variety of spectroscopic tools to understand their electronic structure and its effects on reactivity. The lessons learned from these studies will be used to ultimately develop molecular catalysts for chemical processes of importance in today's world.

In a biochemical context, we will study interactions and transformations involving bioinorganic molecules. One topic of interest regards the properties and reactivity of protein-embedded clusters. Metal clusters perform a variety of biological functions, ranging from electron transfer and signaling to catalysis of complex transformations. Our initial focus will be on the biochemistry of iron-sulfur clusters. Proteins displaying iron-sulfur clusters will be expressed in high yields to allow for active site engineering and reactivity studies. These studies will improve our understanding of the strategies evolved by Nature to facilitate chemical transformations using metal clusters. One potential application will be the design of biocatalysts for the generation of fuels from water or carbon dioxide.

Papers

12)	Theodor Agapie, Sandy Suseno, Joshua J. Woodward, Stefan Stoll, R. David Britt, and Michael A. Marletta “NO formation by a catalytically self-sufficient bacterial nitric oxide synthase from Sorangium cellulosums” Proc. Natl. Acad. Sci. USA 2009, 106(38), 16221-16226 link
11)	Theodor Agapie, Michael W. Day, and John E. Bercaw “Synthesis and Reactivity of Tantalum Complexes Supported by Bidentate X2 and Tridentate LX2 Ligands having Two Phenolates Linked to Pyridine, Thiophene, Furan, and Benzene Connectors – Mechanistic Studies of the Formation of a Tantalum Benzylidene and Insertion Chemistry for Tantalum Carbon Bonds” Organometallics 2008, 27(23), 6123-6142 link
10)	Theodor Agapie, Lawrence M. Henling, Antonio G. DiPasquale, Arnold L. Rheingold, and John E. Bercaw “Zirconium and Titanium Complexes Supported by Tridentate LX2 Ligands having Two Phenolates Linked to Furan, Thiophene, and Pyridine Donors: Precatalysts for Propylene Polymerization and Oligomerization” Organometallics 2008, 27(23), 6245-6256 link
9)	Theodor Agapie, Jay A. Labinger, and John E. Bercaw “Mechanistic Studies of Olefin Trimerization with Chromium Catalysts – Deuterium Labeling and Studies of Regiochemistry Using a Model Cromacyclopentane Complex” J. Am. Chem. Soc. 2007, 129(46), 14281-14295 link
8)	Theodor Agapie and John E. Bercaw “Cyclometallated Tantalum Diphenolate Pincer Complexes: Intramolecular C-H/M-CH3 σ– Bond Metathesis May Be Faster than O-H/M-CH3 Protonolysis" Organometallics 2007, 26(12), 2957-2959 link
7)	Smaranda C. Marinescu, Theodor Agapie, Michael W. Day, and John E. Bercaw "Group 3 Dialkyl Complexes with Tetradentate (L, L, N, O; L = N, O, S) Monoanionic Ligands – Synthesis and Reactivity" Organometallics 2007, 26(5), 1178-1190 link
6)	Theodor Agapie, Michael W. Day, Lawrence M. Henling, Jay A. Labinger, and John E. Bercaw “A Chromium Diphosphine System for Catalytic Ethylene Trimerization: Synthetic and Structural Studies of Chromium Complexes with a Nitrogen-Bridged Diphosphine Ligand with ortho-Methoxyaryl Substituents” Organometallics 2006, 25(11), 2733-2742 link
5)	Theodor Agapie, Susan J. Schofer, Jay A. Labinger, and John E. Bercaw “Mechanistic Studies of the Ethylene Trimerization Reaction with Chromium – Diphosphine Catalysts: Experimental Evidence for a Mechanism Involving Metallacyclic Intermediates” J. Am. Chem. Soc. 2004, 126(5), 1304-1305 link
4)	Theodor Agapie, Paula L. Diaconescu, and Christopher C. Cummins “Methine (CH) Transfer via a Chlorine Atom Abstraction/Benzene-Elimination Strategy: Molybdenum Methylidyne Synthesis and Elaboration to a Phosphaisocyanide Complex” J. Am. Chem. Soc. 2002, 124(11), 2412-2413 link
3)	Theodor Agapie, Paula L. Diaconescu, Daniel J. Mindiola and Christopher C. Cummins “Radical Scission of Symmetrical 1,4-Dicarbonyl Compounds: C-C Bond Cleavage with Titanium(IV) Enolate Formation and Related Reactions” Organometallics 2002, 21(7), 1329-1340 link
2)	Paula L. Diaconescu, Aaron L. Odom, Theodor Agapie and Christopher C. Cummins “Uranium-Group 14 Element Single Bonds: Isolation and Characterization of a Uranium(IV) Silyl Species” Organometallics 2001, 20(24), 4993-4995 link
1)	Theodor Agapie, Aaron L Odom, Christopher C. Cummins “In Pursuit of the Molybdenum(III) Tris(thiolate) Fragment: Unusual Structure of a Dimolybdenum μ -Nitrido Complex" Inorg. Chem. 2000, 39(2), 174-179 link

Patents

1)	Theodor Agapie, Suzanne Golisz, Daniel Tofan, and John E. Bercaw "Olefin Polymerization Catalysts Based on Semirigid Tridentate Ligands" provisional patent 60/846385.

Principal Investigator

Theodor Agapie was born in 1979 in Bucharest, Romania. He received his B.S. degree from Massachusetts Institute of Technology in 2001 and his Ph.D. from California Institute of Technology in 2007. Upon completion of his Ph.D. he moved to University of California, Berkeley as a Miller Postdoctoral Fellow.

Theo developed his passion for chemistry during high school and participated in chemistry competitions; he won two silver medals at the International Chemistry Olympiads as part of the Romanian team. While an undergraduate at MIT, he worked with Professor Christopher C. Cummins for more that three and a half years on atom and fragment transfer chemistry involving metal complexes, on titanium-ketyl radical chemistry, and on DFT computations to detail the electronic structure of synthesized complexes. At graduation, he received the Chemistry Department's Alpha Chi Sigma Award for achievement in research, scholarship, and service to the department. At Caltech, Theo worked under the tutelage of Professor John E. Bercaw on mechanistic and synthetic aspects of chromium-based olefin oligomerization catalysis and on developing new early transition metal nonmetallocene olefin polymerization catalysts. His Ph.D. thesis received Caltech's Chemistry Department Herbert Newby McCoy Award for outstanding contribution to the science of chemistry. Upon graduation, in May 2007, Theo moved to UC Berkeley to work with Professor Michael A. Marletta as a Miller Institute Fellow. There, he focused on mechanistic aspects of biochemical nitric oxide synthesis involving the metalloprotein nitric oxide synthase.

Theo returned to Caltech on February 11, 2009 to start his independent career as an assistant professor of chemistry.

Graduate Students

	Steven Chao University of Texas '08 Chemistry B.S. stchao
	Paul Kelley Catholic University of America '08 Biochemistry B.S. egadsman
	Sibo Lin Indiana University '08 Chemistry B.S. sibolin
	Madalyn Radlauer Stanford '08 Chemistry B.S. madalyn
	Emily Tsui MIT '08 Chemistry B.S. etsui

Undergraduate Students

	Nadia Lara Caltech '12 lara
	Eva Nichols Caltech '12 eva
	Jade Shi Caltech '12 jadeshi
	Alexandra Velian Caltech '09 velian
	Andreas Wierschen UNC '11 awiersch