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Chemistry A250A
Mindiola Group Website

Professor Mindiola began his college education at Michigan State University, East Lansing, MI, in 1992. As a "Spartan", he spent the next three and a half years learning the crafts of inorganic chemistry under the auspices of Professor Kim R. Dunbar. After obtaining his B.S. degree in chemistry from MSU in 1996, Professor Mindiola then attended the Massachusetts Institute of Technology in Cambridge, MA, under the guidance of Professor Christopher "Kit" Cummins. In the summer of 2000, Daniel completed his Ph. D. degree and continued work in small molecule chemistry as an NIH and FORD post-doctoral fellow in the laboratories of Professor Gregory L. Hillhouse at the University of Chicago. In 2002, he accepted an invitation to join the Chemistry Faculty at Indiana University in the city of Bloomington, IN, and was promoted to Associate Professor with tenure in 2007.

Mindiola's research work entails the design and assembly of reactive metal complexes of early metals and their role in unusual transformations such as C-H activation and C-N bond cleavage reactions. He is also interested in novel catalytic processes mediated by reactive complexes containing metal-ligand multiple bonds.

Research

One of our main themes in the group is the assembly of low- coordinate complexes containing metal-ligand multiple bonds. We have discovered that one-electron oxidation processes can readily induce α-hydrogen abstraction concomitant with formation of the metal- ligand multiple bond. As a result, our group has developed synthetic strategies to generate low-coordinate metal complexes containing terminal alkylidene, alkylidyne, and imide functionalities. As expected, these functionalities are highly reactive, and can engage in group transfer, and intermolecular C-H bonds of arenes and alkanes (under mild conditions). In general, early-transition metal alkylidenes are exceedingly nucleophilic, and our group has used this intrinsic property to achieve terminal metal imides, and phosphinidenes from the corresponding alkylidene motif. Our group has also demonstrated that terminal imides and phosphinidenes can be powerful carboamination catalysts as well as group-transfer reagents.

In addition to synthesis and catalysis, our research group is interested in studying low-coordinate transition metal complexes capable of activating and cleaving strong nitrogen-carbon bonds in N- heterocyclic molecules. We are particularly interested in complexes composed of Ti, V, Nb, and Mo. For instance, our group has discovered that unsaturated complexes containing terminal M=CHR and M≡CR linkages can readily ring-open the C-N bond of N- heterocycles such as pyridine and picolines. These reactions are important to many industrial processes, such as the catalytic activation and removal of nitrogen (as NH₃) from coal-based liquids.

Mechanistic details surrounding metal-mediated N-C bond cleavage are important to understanding hydrodenitrogenation (HDN) since the metal's role in promoting this reaction still remains uncertain.

Shown to the left is the molecular structure of the first four- coordinate titanium alkylidene and vanadium alkylidyne species. The sterically demanding β-diketiminate ligand (space filled) provides sufficient protection to allow for a low-coordinate environment. These systems contain the shortest Ti=C (~1.83 Å) and V≡C (~1.67 Å) bonds ever reported and display highly nucleophilic character at carbon.

Publications

"Structural, Spectroscopic and Theoretical Elucidation of a Redox Active Pincer-Type Ancillary Applied in Catalysis." Debashis Adhikari, Susanne Mossin, Falguni Basuli, John C. Huffman, Robert K. Szilagyi, Karsten Meyer, and Daniel J. Mindiola, J. Am. Chem. Soc. 2008, 130, 3676-3682.

"A Transient VIII Alkylidene Complex. Oxidation Chemistry Including the Activation of N2 to Afford a Highly Porous Honeycomb-Like Arrangement." Uriah J. Kilgore, Caitlin A. Sengelaub, Maren Pink, Alison R. Fout, and Daniel J. Mindiola, Angew. Chem. Int. 2008, 47, 3769-3772.

"Early-Transition Metal Hydrazidos: Masked Metallanitrenes from N-N Bond Scission." Daniel J. Mindiola, Angew. Chem. Int. Ed. (Invited "Highlights" article). 2007, 47, 1557-1559.

"Structural Elucidation of a Nickel Boryl Complex. A Recyclable Borylation Ni(II) Reagent of Bromobenzene." Debashis Adhikari, John C. Huffman, and Daniel J. Mindiola, Chem. Commun. 2007, 4489-4491.

"An Alkylidyne Analogue of Tebbe’s Reagent. Trapping Reactions of a Titanium Neopentylidyne by Incomplete and Complete 1,2-Additions." Brad C. Bailey, Alison R. Fout, Hongjun Fan, John Tomaszewski, John C. Huffman, and Daniel J. Mindiola, Angew. Chem. Int. Ed. 2007, 46, 8246-8249.

"Cyclic Homogeneous Denitrogenation of N-Heterocycles Applying a Titanium Reagent." Alison R. Fout, Brad C. Bailey, John Tomaszewski, and Daniel J. Mindiola, J. Am. Chem. Soc. 2007, 129, 12640-12641.

"Niobium Bis-Alkylidene Complexes Prepared by a Multi-Electron Redox Process." Uriah J. Kilgore, John Tomaszewski, Hongjun Fan, John C. Huffman, and Daniel J. Mindiola, Organometallics 2007, 26, 6132-6138.

"Intermolecular C-H Bond Activation Reactions Promoted by Transient Titanium Alkylidynes. Synthesis, Reactivity, Kinetic, and Theoretical Studies of the Ti=C^tBu Linkage." Brad C. Bailey, Hongjun Fan, John C. Huffman, Mu-Hyun Baik, and Daniel J. Mindiola, J. Am. Chem. Soc. 2007, 129, 8781-8793.

"Snapshots of an Alkylidyne for Nitride Triple Bond Metathesis." Brad C. Bailey, Alison R. Fout, Hongjun Fan, John C. Huffman, J. Brannon Gary, Marc J. A. Johnson, and Daniel J. Mindiola, J. Am. Chem. Soc. 2007, 129, 2234-2235.

"Intermolecular Activation of C-X (X = H, O, F) Bonds by a Ti=CtBu Linkage." Brad C. Bailey, John C. Huffman, and Daniel J. Mindiola, J. Am. Chem. Soc. 2007, 129, 5302-5303.

"Neutral and Zwitterionic Low-Coordinate Titanium Complexes Bearing the Terminal Phosphinidene Functionality. Structural, Spectroscopic, Theoretical, and Catalytic Studies Addressing the Ti-P Multiple Bond." Guangyu Zhao, Falguni Basuli, Uriah J. Kilgore, Hongjun Fan, Halikhedkar Aneetha, John C. Huffman, Gang Wu, and Daniel J. Mindiola, J. Am. Chem. Soc. 2006, 128, 13575-13585.

"Room Temperature Ring-Opening Metathesis of Pyridines by a Transient Ti=C Linkage." Brad C. Bailey, Hongjun Fan, John C. Huffman, Mu-Hyun Baik, and Daniel J. Mindiola, J. Am. Chem. Soc. 2006, 128, 6798-6799.

Awards

• Alfred P. Sloan Research Fellow, 2005-2007
• Camille and Henry Dreyfus Teacher-Scholar Award, 2005
• 2005 IU Outstanding Junior Faculty Award
• IU Summer Faculty Fellowship, 2004
• 2004 Presidential Early Career Award for Scientists and Engineers
• National Science Foundation Faculty Early Career Development (CAREER) Award, 2003
• Camille and Henry Dreyfus New Faculty Award, 2002
• NIH Postdoctoral Fellow, University of Chicago, 2002
• Ford Foundation Postdoctoral Fellow, University of Chicago, 2001-02

Highlights

• Professor Mindiola was one of twenty NSF-Supported Young Scientists and Engineers to Receive Presidential Early Career Awards at the White House. For more information see http://www.nsf.gov/news/news_summ.jsp?cntn_id=104239.
• Professor Mindiola will be joining the Editorial Advisory Board for the journal “Organometallics” for a period of three years beginning January 1, 2009.