Organic, organometallic, catalysis, bio-organometallic
We are contributing to innovation and understanding in
catalysis, clean energy production, nanotechnology, and medicine.
The importance of catalysis is highlighted by
a recent report, which states that catalysis-based
chemical syntheses are involved in 60% of today's chemical products and 90% of
current chemical processes. In the U.S.,
the chemical industry makes the largest trade
surplus of any non-defense-related sector ($20.4 billion in 1995), represents
10% of all manufacturing, and employs more than 1 million people.
We create catalysts which operate in new ways, transforming organic
molecules more quickly, in higher yield, with fewer by-products and less waste,
contributing to sustainability and green chemistry. Moreover, we are applying what we have learned to new ways to make hydrogen from renewable resources.
In separate research
projects, we are using organic synthesis to make contributions to
nanotechnology and health care.
Specific research areas are:
- bifunctional organometallic
catalysts for the enhanced reaction of non-polar organics with polar reactants such
as water (funding: NSF and San Diego Foundation)
- synthesis of MRI contrast
agents for diagnosis of cancer and evaluation of nanodevices (funding: NIH)
- catalysts to produce hydrogen directly from water, and use hydrogen in fuel cells
- metal complexes of ketenes and carbenes
(past funding: NSF, Petroleum Research Foundation)
- gas-phase organometallic
chemistry (past funding: NSF)
- metal complexes of proteins,
peptides, amino acids and other biomolecules
In the first area (catalysis), we
are probing the combined effects of a metal and ligands capable of donating or
accepting protons or hydrogen bonds. As an example of the power of bifunctional
catalysis, we have been able to make catalysts for anti-Markovnikov hydration
of alkynes which are more than 1000 times faster than others reported in the
literature, accomplishing within minutes a reaction that would take more than a
million years to complete without catalyst! A paper from our group was featured
in Chemical and Engineering News (October 4, 2004 issue, page 31). This work has led to a patented catalyst which is sold for research purposes
by Strem Chemicals. In ongoing work, we are trying to understand fully the
reasons for the high activity, productivity, and selectivity of the new
A second example of the power of bifunctional catalysis is shown in eq. 2,
where we find that the catalyst shown can move alkene double bonds up to 30
positions down a chain of carbon atoms, yet shows useful selectivity in
other alkene isomerization reactions. Control experiments showed that the
heterocycle accelerates reactions by factors of up to 10,000. This paper
was recently featured in
and Engineering News (July 23, 2007 issue, page 29).
This and other reactions are the subjects of exciting
investigations in the Grotjahn lab.
In the second area (contrast agents for medical imaging), we are making
molecules which bind gadolinium tightly, while also conferring certain properties
for maximum detection sensitivity in MRI (magnetic resonance imaging). This
work involves total synthesis of compounds with several chiral centers. In
collaboration with researchers at University of Pittsburgh Medical Center,
these molecules are being used to create new nanodevices for the detection of
various forms of cancer. In addition, we are trying to answer fundamental
questions about the ways in which nanoparticles are metabolized by the body.
Students in my group are exposed to a wide variety of techniques: Organic
synthesis is used to make new ligands, inorganic and organometallic chemistry
are used to make new metal complexes, and NMR spectroscopy is used extensively
to study reactants and products. In fact, we run many reactions inside NMR
tubes because we can easily detect some sensitive reaction intermediates. Many
complexes are air-sensitive, so students in my group learn how to handle
compounds in inert-atmosphere glove boxes or in Schlenk apparatus. In addition,
we are now using combinatorial methods to screen ever-larger numbers of
Students graduating from my group enjoy a thorough preparation in fields
such as organic synthesis, catalysis, spectroscopy, organometallics,
coordination chemistry, and computational chemistry. Students with different
interests and preferences can emphasize any or all of these areas in their
work. In the area of organic synthesis, we work with a wide variety of heterocycles
and other nitrogen-containing compounds, organolithiums and other polar organometallics,
phosphines, and chiral compounds, to name a few compound classes. Our group
strives to publish in high-profile, internationally respected journals such as J.
Am. Chem. Soc., Angewandte Chemie, etc. My graduate students have
gone on to postdoctoral positions and permanent jobs in the pharmaceutical
industry, national labs, or universities. Undergraduates from my group have
gone on to either jobs using their organic and organometallic skills, or to
graduate programs at institutions such as Harvard, Scripps Research Institute,
and UC Irvine.
- "Stereoselective Alkene Isomerization over One Position"
Larsen, Casey R.; Grotjahn, Douglas B.,
J. Am. Chem. Soc. 2012, 134 10357-10360.
- "PLGA nanoparticle-mediated delivery of tumor antigenic peptides elicits effective immune responses"
Ma, Wenxue; Chen, Mingshui; Kaushal, Sharmeela; et al.,
International J. Nanomedicine 2012, 7 1475-1487.
- "Evolution of Iridium-Based Molecular Catalysts during Water Oxidation with Ceric Ammonium Nitrate"
Grotjahn, Douglas B.; Brown, Derek B.; Martin, Jessica K.; et al.,
J. Am. Chem. Soc. 2011, 133 19024-19027.
- "Enabling Bifunctionality and Hemilability of N-Heteroaryl NHC Complexes"
Specht, Zephen G.; Cortes-Llamas, Sara A.; Tran, Hai N.; et al.,
Chemistry-A European J. 2011, 17 6606-6609.
- "A Labile and Catalytically Active Imidazol-2-yl Fragment System"
Miranda-Soto, Valentin; Grotjahn, Douglas B.; Cooksy, Andrew L.; et al.,
Angewandte Chemie 2011, 50 631-635.
- "Unexpected synthesis and structural characterization of Pt( II)Cl-2-1,5-hexadiene from reaction of allyl chloride and K2PtCl4
Nair, Reji N.; Golen, James A.; Rheingold, Arnold L.; et al.,
Inorganica Chimica Acta 2010, 364 272-274.
- "A Fluorinated Dendrimer-Based Nanotechnology Platform New Contrast Agents for High Field Imaging"
Huang, Zhihua; Sengar, Raghvendra S.; Nigam, Archana; et al.,
Investigative Radiology 2010, 45 641-654.
- "Bifunctional Organometallic Catalysis and Reactivity Using Heterocyclic Phosphines and Metallated Heterocycles"
Grotjahn, Douglas B.,
Chemistry Letters 2010, 39 908-914.
- "Structures, Mechanisms, and Results in Bifunctional Catalysis and Related Species Involving Proton Transfer"
Grotjahn, Douglas B.,
Topics in Catalysis 2010, 53 1009-1014.
- "New Insights on Kinetic Versus Thermodynamic Ratios in Catalyzed Alkene Isomerization"
Larsen, Casey R.; Grotjahn, Douglas B.,
Topics in Catalysis 2010, 53 1015-1018.
- "One-Pot Formation of Functionalized Indole and Benzofuran Derivatives Using a Single Bifunctional Ruthenium Catalyst"
Nair, Reji N.; Lee, Paul J.; Grotjahn, Douglas B.,
Topics in Catalysis 2010, 53 1045-1047.
- "Catalysis of Selective Hydrogen/Deuterium Exchange at Allylic Positions Using Deuterium Oxide"
Erdogan, Gulin; Grotjahn, Douglas B.,
Topics in Catalysis 2010, 53 1055-1058.
- "Single Bifunctional Ruthenium Catalyst for One-Pot Cyclization and Hydration giving Functionalized Indoles and Benzofurans"
Nair, Reji N.; Lee, Paul J.; Rheingold, Arnold L.; et al.,
Chemistry-A European J. 2010, 16 7992-7995.
- "Multimodal Study of Secondary Interactions in (CpIr)-Ir-star Complexes of Imidazolylphosphines Bearing an NH Group,"
with J. E. Kraus, H. Amouri, et al.,
J. Am. Chem. Soc. 2010, 132 7919-7934.
- " Heteroatoms moving protons: Synthetic and mechanistic studies of bifunctional organometallic catalysis,"
Pure and Applied Chemistry 2010, 82 635-647.
- "Production and characterization of monoclonal anti-sphingosine-1-phosphate antibodies,"
with N. O'Brien, S. T. Jones, D. G. Williams, et al.,
Journal of Lipid Research 2009, 50 2245-2257.
- "Mild and Selective Deuteration and Isomerization of Alkenes by a Bifunctional Catalyst and Deuterium Oxide,"
with G. Erdogan
J. Am. Chem. Soc. 2009, 131 10354.
- "Bifunctional catalysts and related complexes:
structures and properties,"
invited Perspectives article for Dalton Trans.
- "Imidazol-2-yl Complexes of Cp*Ir as Bifunctional
with Valentin Miranda-Soto, Antonio G. DiPasquale and Arnold L. Rheingold,
J. Am. Chem. Soc. 2008, 130, 13200-13201
- "Finding the Proton in a Key Intermediate
of anti-Markovnikov Alkyne Hydration by a Bifunctional Catalyst,"
with Elijah J. Kragulj, Constantinos D. Zeinalipour-Yazdi, Valentin
Miranda-Soto, Daniel A. Lev, and Andrew L. Cooksy,
J. Am. Chem. Soc. 2008, 130,
- "Hydrogen Bond Acceptance of Bifunctional Ligands
in an Alkyne-Metal π Complex,"
with Valentin Miranda-Soto, Elijah J. Kragulj, Daniel A. Lev, Gulin Erdogan,
Xi Zeng, and Andrew L. Cooksy
J. Am. Chem. Soc. 2008, 130,
- "Extensive Isomerization of Alkenes using a Bifunctional
Catalyst: An Alkene Zipper," with Casey R. Larsen, Jeffery L. Gustafson, Reji Nair,
and Abhinandini Sharma, J. Am. Chem. Soc. 2007, 129,
- "Experimental and Computational Study of the Transformation of
Terminal Alkynes to Vinylidene Ligands on trans-(Chloro)bis(phosphine)Rh
Fragments and Effects of Phosphine Substituents," with Xi Zeng, Andrew L. Cooksy,
W. Scott Kassel, Antonio G. DiPasquale, Lev. N. Zakharov, and Arnold L.
Rheingold, Organometallics 2007, 26, 3385-3402.
- "Bifunctional Imidazolylphosphine Ligands as Hydrogen Bond Donors
Promote N-H and O-H Activation on Platinum," with Yi Gong, Antonio G. DiPasquale,
Lev N. Zakharov, and Arnold L.Rheingold, Organometallics 2006,
25, 5693-5695. [one of
the 20 most-accessed articles in Organometallics published between
September and December, 2006]
- "Alkyne-to-vinylidene Transformation on trans-(Cl)Rh(phosphine)2:
Acceleration by a Heterocyclic Ligand and Absence of Bimolecular
Mechanism," with Xi Zeng and Andrew L. Cooksy, J. Am. Chem. Soc. 2006,
- "Changes in Coordination of Sterically Demanding Hybrid Imidazolylphosphine
Ligands on Pd(0) and Pd(II)," with Yi Gong, Lev Zakharov, James A. Golen, and
Arnold L. Rheingold, J. Am. Chem. Soc. 2006, 128, 438-453.
Organometallic Catalysts involving Proton Transfer or Hydrogen Bonding," a
Concepts article in Chemistry – a European Journal, 2005, 11, 7147-7153.
- "A general bifunctional catalyst for the anti-Markovnikov hydration of
terminal alkynes to aldehydes gives enzyme-like rate and selectivity
enhancements," with Daniel A. Lev, J. Am. Chem. Soc. 2004,
126, 12232-12233. [see also "Organometallic catalysts are enzyme-like," Science and Technology
Concentrates section of Chemical and Engineering News, 4 October 2004 issue, page 31.]
Synthesis, Submillimeter Spectra, and Precise Structure of Monomeric,
Solvent-Free CuCH3," with DeWayne T. Halfen, Lucy M. Ziurys, and Andrew L.Cooksy, J. Am. Chem. Soc. 2004, 126, 12621-12627.
- "Double C-H
activation during functionalization of phenyl(methyl)ketene on iridium(I) using
alkynes. A synthesis of 1,4-dien-3-ones," with Justin M. Hoerter and John
L. Hubbard, J. Am. Chem. Soc. 2004, 126, 8866-8867.
- "Controlled, Reversible Conversion of a Ketene Ligand to Carbene and CO Ligands
on a Single Metal Center," with Galina A. Bikzhanova, Laura S. B. Collins,
Thomas Concolino, Kin-Chung Lam, and Arnold L.Rheingold, J. Am. Chem. Soc.
5222-5223. [see also "Ketene ligand cleaved
to carbene and CO ligands reversibly," Science and Technology
Concentrates section of Chemical and Engineering News, 29 May 2000 issue, page 52. "Of Ketenes and Carbenes," Highlights of the Recent
Literature, Editor's Choice, Science, 2 June 2000 issue, vol. 288, page 154. "Metal-Assisted Cleavage of a C-C
Double Bond: Simple and Reversible," by H. Werner and E. Bluel, Highlights
section of Angewandte Chemie, Int. Ed. Engl. 2001, 40,
of CH3K in the Gas Phase: Structural and Mechanistic Trends for Monomeric,
Unsolvated CH3M and HCCM (M = Li, Na, K)," with T. C. Pesch, M.
A. Brewster, and L. M. Ziurys, J. Am. Chem. Soc. 2000, 122, 4735-4741.
- "High Arenophilicity
and Water Tolerance in Direct Derivatization of Peptides and Proteins by Metal
p-Coordination," with Camil Joubran, David
Combs, and Daniel C. Brune, J. Am. Chem. Soc. 1998,
Recently graduated students and postdocs
and where they went after SDSU
Full Publications List
- Yi Gong, Ph.D. – Solvay, Los Angeles, CA
- Allan Mallari, B.S. – Materia, Pasadena, CA
- Tiffany Hoerter, M.S. – AstraZeneca, Wilmington, DE
- Justin Hoerter, postdoc – DuPont, Wilmington, DE
- Dan Lev, Ph.D. – Ropes and Gray, Boston; J.D., Northwestern University Law School
- Robin Hurt, B.S. – Ph.D. program, UC Irvine
- Shirley Leung, M.S. – Novartis, Boston, MA
- Xi Zeng, M.S. – Diazyme Laboratories / General Atomics, San Diego, CA
- Jeff Gustafson, B.S. – Ph.D. program, Yale
- Christie Schulte, B.S. – GlaxoSmithKline, North Carolina