John Bleeke

John Bleeke

​Professor of Chemistry
Director of Undergraduate Studies in Chemistry
PhD, Cornell University
MS, Cornell University
BA, Carthage College
research interests:
  • Mechanistic Studies of Transition Metal Mediated Reactions
  • Metallabenzenes and Other Aromatic Metallacycles
  • Synthesis and Reactivity of Transition Metal Organometallic Compounds
  • Organic Chemistry of Metal Bound Polyenyl Ligands

contact info:

mailing address:

  • Washington University
    CB 1134
    One Brookings Dr.
    St. Louis, MO 63130-4899

Since joining the chemistry faculty in 1981, Profesor Bleeke has established a nationally and internationally recognized research program in the area of transition metal organometallic chemistry. He is particularly well known for his research with metallabenzenes and other aromatic metallacycles.

Ever since Kekule’s intuitive idea on the structure of benzene, “aromaticity” has been one of the most fascinating and provocative research topics in chemistry. While benzene is the archetypical aromatic compound, it is now well known that heterocyclic analogues of benzene containing N, O, P or S also exhibit aromatic properties. In contrast very little is known about metallacyclic benzenoid compounds, i.e., benzene analogues in which a CH group has been formally replaced by a transition metal and its associated ligands. Such “metallabenzenes” represent a fundamentally new class of aromatic compounds in which metal d orbitals participate fully with carbon p orbitals in the formation of ring pi-bonds. We have succeeded in synthesizing metallabenzenes using an approach that employs pentadienyl reagents as the source of ring carbon atoms and C-H bond activation in the key ring-forming step. Using this strategy, we have synthesized red crystalline “iridabenzene” (see figure 1) in high yield. 

X-ray crystallography of 1 has confirmed the presence of a fully delocalized (and almost planar) metallacyclic ring, while the 1H NMR spectrum exhibits downfield chemical shifts, consistent with the presence of an aromatic ring current. Iridabenzene 1 exhibits a rich and varied reaction chemistry. Some of these reactions are typical of conventional organic arenes while others differ sharply due to the powerful influence of the transition metal center.

More recently, we have begun to study the synthesis of heteroatom-containing analogues of 1, species such as irdidafuran, iridapyrylium, iridathiophene, iridathiabenzene, and iridapyrrole. Our goal is to generate a family of closely-related molecules, enabling us to assess the effects of ring size and heteroatom incorporation on stability, structure, spectroscopy, and reactivity. 

Selected Publications

J.R. Bleeke, “The First Iridabenzenes: Synthesis, Properties, and Reactions,” Chapter 2 in Metallabenzenes: An Expert View, L.J. Wright, Editor, John Wiley & Sons, Chichester, UK (2017).

J.R. Bleeke, M. Stouffer, and N.P. Rath, “Synthesis, Spectroscopy, Structure, and Reactivity of Bis-Azapentadienyl-Ruthenium-Phosphine Complexes,” J. Organomet. Chem., 781, 11-22 (2015). doi: 10.1016/j.jorganchem.2015.01.006.

J.R. Bleeke, W. Anutrasakda, and N.P. Rath, “Synthesis, Spectroscopy, Structure, and Reactivity of Azapentadienyl-Rhodium-Phosphine and Azapentadienyl-Iridium-Phosphine Complexes,” Organometallics, 32, 6410-6426 (2013). doi: 10.1021/om400765h.

J.R. Bleeke, W. Anutrasakda, and N.P. Rath, “Synthesis, Structure, Spectroscopy, and Reactivity of Azapentadienyl-Cobalt-Phosphine Complexes,” Organometallics, 31, 2219-2230 (2012). doi: 10.1021/om2011326.

J.R. Bleeke, B.L. Lutes, M. Lipschutz, D. Sakellariou-Thompson, J.S. Lee, and N.P. Rath, “Synthesis, Structure, Spectroscopy, and Reactivity of Oxapentadienyl-Cobalt-Phosphine Complexes,” Organometallics, 29, 5057-5067 (2010). doi: 10.1021/om100361a.

J.R. Bleeke, B.L. Lutes, and N.P. Rath, “Synthesis, Structure, Spectroscopy, and Reactivity of Thiapentadienyl-Cobalt-Phosphine Complexes,” Organometallics, 28, 4577-4583 (2009). doi: 10.1021/om9004912.

J.R. Bleeke, P. Putprasert, T. Thananatthanachon, and N.P. Rath, “Synthesis and Characterization of Fused-Ring Iridapyrroles,” Organometallics, 27, 5744-5747 (2008). doi:10.1021/om8008712

J.R. Bleeke, “Aromatic Iridacycles,” Acc. Chem. Res., 40, 1035-1047 (2007). doi: 10.1021/ar700071p.

J.R. Bleeke, “Synthesis and Reactivity of Heteropentadienyl—Transition-Metal Complexes,” Organometallics, 24, 5190-5207 (2005). doi: 10.1021/om058044+.

J.R. Bleeke, “Metallabenzenes,” Chem. Rev., 101, 1205-1227 (2001). doi: 10.1021/cr990337n.

Awards and Recognitions

Panelist, NSF Graduate Fellowship Selection Committee, 2008-2013

Director, Washington University Beckman Scholars Program, 2006-2009

25 Year Service Award from Washington University, 2006

Special Recognition for Excellence in Mentoring, Graduate Student Senate, Washington University, 2004-2005

Member, Executive Committee, NSF ChemLinks Coalition, 1995-1996

Member, Editorial Advisory Board, Organometallics, 1993-1995

Member, Executive Committee, Pew Midstates Consortium for Math and Science, 1989-present

Faculty Mentor for Pew Teacher-Scholar (Postdoctoral Program), 1989-1990

National Science Foundation Predoctoral Fellow, 1976-1979

Cornell Debye Fellow, 1976

National Merit Scholar, 1972