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John J. Eisch
- Distinguished Professor, Organic Chemistry
CONTACT INFORMATION:

Department of Chemistry
State University of New York at Binghamton
Binghamton, NY 13902

e-mail : jjeisch@binghamton.edu
Phone : (607) 777 4261
Fax : (607) 777 4478

PROFESSIONAL BACKGROUND


• B.S., summa cum laude, Marquette University, 1952
• Ph.D., Iowa State University, 1956, with Professor Henry Gilman
• Postdoctoral Fellow with Nobel Laureate Karl Ziegler, Max Planck Institut für Kohlenforschung (Mülheim), Germany 1956 -1957
• European Research Associates Fellow, Brussels, Belgium 1957, Union Carbide Corp.
• Research Fellow, Japan Society for the Promotion of Science, 1979, Kyoto University
• Alexander von Humboldt Senior Scientist Research Award, Universität München, Germany 1993-1996
• First Henry Gilman Research Award, Iowa State University, 1995
• Doctor of Science, honoris causa, Marquette University, 2002
RESEARCH INTERESTS

Our current research embraces a variety of studies on synthesis and reaction mechanism in organometallic and heterocyclic chemistry. Such interests in organometallic chemistry encompass the following aspects: 1) the stereoselective formation of carbon-carbon and carbon-hydrogen bonds by means of main-group or transition metal alkyls; 2) fundamental studies of Ziegler-Natta catalytic alkylations and oligomerizations, essential to industrial polymer and hydrocarbon technology; 3) the utility of subvalent organotransition-metal reagents in organic synthesis, especially in the homogenous desulfurization of sulfides and thiols (important for future chemical processes based on coal); 4) the generation of subvalent early transition metal reductants and their utility in organic synthesis and catalysis; and 5) unusual pericyclic or anionic rearrangments, such as those interconverting various transition metal, boron and aluminum compounds or the 1,n shifts observed in silicon and lithium compounds. Finally, this investigator has edited and composed Volumes 2, 3, and 4 of "Organometallic Syntheses," a treatment of research techniques and a compilation of reliable synthetic procedures for many organometallic compounds.

In heterocyclic studies we have been concerned with the synthesis and properties of unusual rings containing metals or nitrogen as ring constituents. Illustrative are five-membered (borole) and seven-membered (borepin) boron rings, which display antiaromatic and aromatic character, respectively. Furthermore, nitrogen heterocycles isoelectronic with azulenes have been found to display chromoisomerism (tautomeric equilibira between colorless and highly colored isomers), and the highly reactive, antiaromatic dibenzazapentalene and 1,2-diazacyclobutadiene systems have been synthesized for the first time. The results of such studies are expected to shed light on pi-electron interactions between carbon centers and various potential pi-bonding metals or nitrogen centers.

A most recent developing interest in our research has been a study of how amino acids, sugars and lipids were evolved on the prebiotic earth, thereby setting the stage for the chemical evolution of the RNA World and the emergence of Life. Particular attention has been given to the elaboration of sugar alcohols from the transition metal-catalyzed, photochemical redox reactions of formaldehyde.
SELECTED PUBLICATIONS

  1. "Dimerizing or Cyclizing C?C Bond Formation via C?H Activation by Prior Zirconation", J.J. Eisch and S. Dutta, Organometallics, 23, 4181-4183 (2004).

  2. "The Potential of Photochemical Transition Metal Reactions in Prebiotic Organic Synthesis. I. Observed Conversion of Methanol into Ethylene Glycol as Possible Prototype for Sugar Alcohol Formation", J.J. Eisch, P.R. Munson and J.N. Gitua, Origins Life Evol. Biosphere, 34, 441-454 (2004).

  3. "Catalyst Systems for the Polymerization of Olefins and the Stereoregular Polymerization of alpha-Olefins via Metallocyclic Intermediates", John J. Eisch and John N. Gitua, U.S. Patent No. 6,743,872, June 1, 2004

  4. "The Synthesis and Reactivity of Group 4 Zwitterionic Complexes of the Type, M+tCH2AlCl3¯ : One-Component Stereoselective Polymerization and Oligomerization Catalysts for Olefins and Acetylenes, J.J. Eisch and P.O. Otieno, Eur. J. Org. Chem., 3269-3276 (2004).

  5. "Highly Active and Stereoselective Olefin Polymerization Catalysts Generated by the Transfer-Epimetallation of Olefins or Acetylenes with Dialkyltitanium(IV) Complexes: Three-membered Metallocycles as Active Catalyst Sites", J.J. Eisch, J.N. Gitua, P.O. Otieno and A.A. Adeosun, Macromolecular Symposia, 213, 187-198 (2004).

  6. "Mechanism of the Kulinkovich Cyclopropanol Synthesis: Transfer-Epititanation of the Alkene in Generating the Key Titanacyclopropane Intermediate", J.J. Eisch, A.A. Adeosun and J.N. Gitua, Eur. J. Org. Chem, 4721-4727 (2003).

  7. “Stereoselective Olefin Polymerization Catalysts Generated by the Transfer-Epimetalation of Olefins or Acetylenes with Dialkyltitanium(IV) Complexes: Three-Membered Metallocycles as Proposed Chiral Sites”, J.J. Eisch and J.N. Gitua, Organometallics, 22, 4172- 4174 (2003).

  8. "Coordination-Induced Reductive Elimination and Titanium(II) Carbenoid Transfer in Reactions of Dialkyltitanium(IV) Complexes with Unsaturated, Organic Substrates", J.J. Eisch and J.N. Gitua, Organometallics, 22, 24-26 (2003).

  9. "Astonishing Alkylation and Unusual Reduction Reactions of Anionic Titanium(II) Isopropoxide Complexes: Evidence for SET Processes in Transition-Metal Oxidative Additions", J.J. Eisch and J.N. Gitua, Eur. J. Inorg. Chem., 3091-3096 (2002).

  10. “Henry Gilman: American Pioneer in the Rise of Organometallic Chemistry in Modern Science and Technology”, J.J. Eisch, Organometallics, 21, 5439-5463 (2002).

  11. “Electronic and Steric Design of Novel Group 13 Lewis Acids and their Synthesis via Metal-Tin Exchange Reactions”, J.J. Eisch, P.O. Otieno, K. Mackenzie and B. Kotowicz, Advances in Chemistry Series, No. 822, Pamela J. Shapiro and David A. Atwood, Eds., American Chemical Society, Washington, D.C, 2002, pp. 88-103.

  12. “Alkylation of Transition Metal Salts as a Fertile and Versatile Approach to Olefin Polymerization Catalysts”, J.J. Eisch, F.A. Owuor, P.O. Otieno, J.N. Gitua, X. Shi and A.A. Adeosun, in Future Technology for Polyolefin and Olefin Polymerization, M. Terano and T. Shino, Eds., Technology and Education Publishers, Tokyo, 2002, pp. 316-326.

  13. “Metalations with Group 4 Alkylmetal(IV) Halides: Expeditious Route to Metallocene and Nonmetallocene Procatalysts”, J.J. Eisch, F.A. Owuor and P.O. Otieno, Organometallics, 20, 4132-4134 (2001).

  14. “Carbon-Carbon Bond Formation via Oxidative-Addition Processes of Titanium(II) Reagents with pi-Bonded Organic Substrates. Reactivity Modifications by Lewis Acids and Lewis Bases”, J.J. Eisch, J.N. Gitua, P.O. Otieno and X. Shi, J. Organomet. Chem., 624, 229-238 (2001).

  15. “Early Transition Metal Carbenoid Reagents in Epimetallation and Metallative Dimerization of Unsaturated Organic Substrates”, J.J. Eisch, J. Organomet. Chem., 617-618, 148-157 (2001).

  16. “Mechanistic Comparison of the Nickel(0)-catalyzed Homo-oligomerization and Co-oligomerization of Alkynes and Nitriles”, J.J. Eisch, X. Ma, K.I. Han, J.N. Gitua and C. Krüger, Eur. J. Inorg. Chem., 77-88 (2001).

  17. “Transition Metal Alkyls as Versatile Precursors of Ziegler-Natta Metallocene and Nonmetallocene Polymerization Catalysts”, J.J. Eisch, F.A. Owuor, P.O. Otieno and A.A. Adeosun, in Progress and Development of Catalytic Olefin Polymerization, T. Sano, T. Uozumi, H. Nakatani and M. Terano, Eds., Technology and Education Publishers, Tokyo, 2000, pp. 88-97.

  18. “Lithium Chromium(I) Dihydride: A Novel Reagent for the Versatile Reductive Metathesis, Reductive Cyclization, Oligomerization or Polymerization of Diverse Organic Substrates”, J.J. Eisch and J.R. Alila, Organometallics, 19, 1211 (2000).

  19. “Organochromium(III) Intermediates in Reductive Dimerizations and Reductive Metatheses of Organic Substrates by Novel Chromium(I) Reagents”, J.J. Eisch and J.R. Alila, Organometallics, 18, 2930 (1999).

  20. "Novel Synthesis of Unbridged, Sterically Substituted Zirconocene Dichlorides from Fulvenes and Dialkylzirconium Dichlorides via Zirconium(IV) Hydride Transfer", J.J. Eisch, F.A. Owuor and X. Shi, Organometallics, 18, 1583 (1999).
 
 
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updated, December 2004