Indiana University Bloomington
Professor Mindiola Professor Mindiola IUB Department of Chemistry

Chemistry @ IU

Faculty & Research

Daniel J. Mindiola

Professor, Chemistry Department
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Daniel Mindiola
Contact Information:
(812) 855-2399
mindiola@indiana.edu
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. He was promoted to Associate Professor with tenure in 2007, and promoted to Full Professor in 2011.

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.

Mindola Research 1

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

PubMed

Room Temperature Dehydrogenation of Ethane to Ethylene. Vincent N. Cavaliere, Marco G. Crestani, Chun-Hsing Chen, Maren Pink, and Daniel J. Mindiola, J. Am. Chem. Soc. 2011, 133, 10700-10703.

Methane Activation and Exchange by Titanium-Carbon Multiple Bonds. Jaime A. Flores, Vincent N. Cavaliere, Dominik Buck, George Chen, Marco G. Crestani, Balazs Pinter, Mu-Hyun Baik, and Daniel J. Mindiola, Chem. Science 2011, 2, 1457-1462.

Carbenes vs. Alkylidenes.Spot the Difference. Daniel J. Mindiola and Jennifer Scott, Nature Chem. 2011, 3, 15-17.

Reactivity Studies of a Masked Three-Coordinate Vanadium(II) Complex. Ba L. Tran, Madhavi Singhal, Hyunsoo Park, Oanh P. Lam, Maren Pink, J. Krzystek, Andrew Ozarowski, Joshua Telser, Karsten Meyer, and Daniel J. Mindiola, Angew. Chem. Int. Ed. 2010, 49, 9871-9875.

Phosphinidene Complexes of Scandium. Powerful PAr Group-Transfer Vehicles to Organic and Inorganic Substrates. Benjamin F. Wicker, Jennifer Scott, José G. Andino, Xinfeng Gao, Maren Pink, and Daniel J. Mindiola J. Am. Chem. Soc. 2010, 132, 3691-3693.

Low-Coordinate and Neutral Nitrido Complexes of Vanadium. Ba L. Tran, Maren Pink, Xinfeng Gao, Hyunsoo Park, and Daniel J. Mindiola, J. Am. Chem. Soc. 2010, 132, 1458-1459.

Synthetic and Mechanistic Studies of Ring-Opening and Denitrogenation of Pyridine and Picolines. Alison R. Fout, Brad C. Bailey, Dominik Buck, Hongjun Fan, John C. Huffman, Mu-Hyun Baik, and Daniel J. Mindiola, Organometallics 2010, 29, 5409-5422.

Phosphinidene Group-Transfer with a Phospha-Wittig Reagent: A New Entry to Transition Metal Phosphorus Multiple Bonds. Uriah J. Kilgore, Hongjun Fan, Maren Pink, Eugenijus Urnezius, John D. Protasiewicz and Daniel J. Mindiola, Chem. Commun. 2009, 4521-4523.

A Tribute to Frederick Nye Tebbe. Lewis Acid Stabilized Alkylidynes, Alkylidenes, and Imides of 3d Early Transition Metals, Jennifer Scott and Daniel J. Mindiola, Dalton Trans. (Invited "Perspective" article and cover of issue), 2009, 8463-8472.

Tellus in, Tellus out: The Chemistry of the Vanadium Bis(telluride) Functionality. Uriah J. Kilgore, Jonathan A. Karty, Maren Pink, Xinfeng Gao, and Daniel J. Mindiola, Angew. Chem. Int. Ed. 2009, 48, 2394-2397.

Dehydrofluorination of Fluorohydrocarbons by Titanium Alkylidynes via Sequential C-H/C-F Bond Activation Reactions. A Synthetic, Structural, and Mechanistic Study of 1,2-CH Bond Addition and β-Fluoride Elimination. Alison R. Fout, Jennifer L. Scott, Deanna L. Miller, Brad C. Bailey, John C. Huffman, Maren Pink, and Daniel J. Mindiola, Organometallics 2009, 28, 331-347.

Awards

  • Japanese Society for the Promotion of Science (JSPS) Fellowship, 2012
  • National Science Council of Taiwan Lecturer, 2011
  • 2010 Recent Alumni Award from the College of Natural Science, Michigan State University
  • 2009 National Fresenius Award (Phi Lamba Upsilon)
  • 2008-2009 Dalton Transactions US Lectureship Award (University of California, Berkeley CA).
  • Friedrich Wilhelm Bessel Research Award, Alexander Von Humboldt Foundation - Friedrich-Alexander University, Erlangen-Nuremberg, Germany 2009.
  • 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
  • Union Carbide Innovation Award, 1998

Highlights