The Chemistry Department at the State University of New York at Binghamton hosted a special symposium in honor of Distinguished Professor John Eisch October 28/29, 2011. This exciting event celebrated chemistry at Binghamton and Professor Eisch’s distinguished nearly 40-year career at Binghamton. Two Nobel Laureate’s (Negishi, 2010 and Hoffman, 1981) and six alumni provided a fitting recognition of the internationally recognized research program in organometallic chemistry that he created in Binghamton. The symposium was a fitting tribute on the occations of Professor Eisch’s retirement and 80th birthday.
Read more at Binghamton University's Inside magazine.
The Symposium is also available on-line at this link. (pdf, 301 KB)
Available below are the abstracts from the Symposium talks along with links to copies of presentations.
Friday, October 28, 2011 - Talks and Activities
Ei-ichi Negishi, Purdue University
2010 Nobel Laureate in Chemistry
"Magical Power of d-Block Transition Metals – Pd-Catalyzed Cross-Coupling and Zr-Catalyzed Asymmetric Carboalumination of Alkenes (ZACA)"
Until recently, the majority of the 24 d-block transition metals had been used as
superior useful and sturdy materials. Half a century ago, a wide range of possibilities
for use of d-block transition metals as catalysts for organic synthesis were recognized.
These opportunities stem from mainly two fundamental properties of the d-block transition
metals: (1) simultaneous presence or availability of one or more filled-nonbonding
(HOMO) and empty (LUMO) valence-shell orbitals, i.e., "carbene-like," often as highly
reactive and yet thermally stable species, (2) ability to undergo ready and reversible
Redox processes under one-set of reaction conditions. These properties have led to
the development of a large number and widely ranging processes including critically
important C–C bond formation reactions proceeding through: (a) reduction elimination
(ex. Pd-catalyzed cross-coupling), (b) carbometalation (ex. ZACA reaction), and C
migration insertion (ex. carbonylation including "oxo" process). In this lecture,
a brief discussion of the Pd-catalyzed cross-coupling (mostly Negishi coupling) will
be followed by a more detailed discussion of the Zr-catalyzed asymmetric
carboalumination of alkenes (ZACA reaction).
download presentation (pdf, 3.2 MB)
Udo H. Brinker, University of Vienna
Former member and Chair of Chemistry Depatrment, Binghamton University
"Laudatio: The Pleasure of Finding Things Out"
download presentation (pdf, 759 KB)
William C. Kaska, University of California at Santa Barbara (retired in 2004 after 40 years on the
PhD, University of Michigan, 1963
“Some Early Aspects of Carbon-Hydrogen Bond Metalation”
Hydrogen-metal exchange ( C-H + R’-M → C-M + R’-H ) is a major reaction in organometallic chemistry. The reaction is controlled by thermodynamic and kinetic factors with the reaction proceeding to favor the weaker carbon acid R’H. Key advances were made during the period of 1950 to 1970 with the discovery that some transition metal complexes could metalate the C-H bond in sp2- and possibly in sp3-bonded hydrocarbons. Attempts to pursue this advance with sp3 carbon-hydrogen bonds did not yield much success until the discovery of transition-metal pincer ligated compounds by G. van Koten and Bernard Shaw. Our group has pursued the pincer-ligand motif since the middle 1970’s with significant success and the story behind this discovery will be recounted.
download presentation (pdf, 867 KB)
Leslie E. Smith, formerly the National Bureau of Standards, currently the National Institute of Standards
and Technology, Gaithersburg, Md.
Director of the Polymers Division and subsequently the Materials Science and Engineering Laboratory (from 1983 until retirement in 2005)
PhD, Catholic University, 1972
“Phenylsilanes to Polymers”
Our early work demonstrated that the conformations of both synthetic and biological polymers could change profoundly upon adsorption from solution onto a solid substrate. These observations have had implications for both the development of the theory and for the design of engineered surfaces used in artificial implants. The use of ellipsometry to measure the extent of this change in conformation was pioneered at The National Bureau of Standards. Furthermore, our work on the measurement of the hydrolytic degradation rates of polyurethane polymers has been significant. In addition to fundamental studies of the rates and protective mechanisms related to the relevant chemical reactions, these studies have valuable applications to practical problems, particularly estimating the useful lifetime of magnetic tape and similar data storage products. A serious source of failure in magnetic tape involves the ester hydrolysis of the polyurethane polymer that binds the magnetic particles to the polyester substrate. We have measured the rate of this reaction, the equilibrium concentrations of the species involved as a function of humidity, and the effects of various additives that can be used to inhibit such reactions. We have also developed a number of practical tests that can be used by archivists and librarians to evaluate the condition of tapes in storage.
download presentation (pdf, 950 KB)
Csaba Kovacs, Eastman Kodak Corporation Research and Development Laboratories, Rochester, N.Y. (from
1974 until retirement in 1999)
PhD, Catholic University, 1972
“Chemical and Personal Rearrangements”
In chemistry, as in life, there are rearrangements that may retain the components, but do change the nature and the behavior of the new product. For most chemists, going through life and its many changes, such rearrangements are just part of living. In this presentation some aspects of bond, Wittig, anionic, structural and personal rearrangements will be touched upon. It will be described how in major companies, like Eastman Kodak, if the appropriate rearrangement does not occur, their future might be bleak. Furthermore, the speaker’s experience as director of research and development for a Chinese nanotechnology company from 2005 to 2010 has represented how confronting change can occur with an Oriental accent. Finally, Dr. Eisch’s influence in rearranging a student’s thought processes will be elucidated.
download presentation (pdf, 1.1 MB)
Peter McGrath, Binghamton University
Acting President Binghamton University
“Congratulations and Thank You”
download presentation (m4v, 24.9 MB)
Wayne E. Jones, Jr., Binghamton University
Chemistry Department Chair, Binghamton University
"A Very Brief Look at John Eisch's Career"
download presentation (pdf, 560 KB)
Saturday, October 29, 2011 - Talks and Activities
Roald Hoffmann, Cornell University
1981 Nobel Laureate in Chemistry
“All the Ways to Have a Bond”
The concept of a chemical bond, so essential to chemistry, and with a venerable history, has life, generating controversy and incredible interest. Even if (or maybe because) we can’t reduce it to physics. I will discuss some of the common experimental criteria for judging the presence and strength of a bond: length, energy, force constants, magnetism, energy splittings and other spectroscopic criteria. On the theoretical side, I will look at bond orders, population analyses, bond critical points, and electron localization functions and will give a personal opinion on the utility of the various measures. My advice at the end is likely to be: Push the concept to its limits. Think about any bond in terms of all the various criteria, experimental and theoretical, that we have discussed. Accept that (at the limits) a bond will be a bond by some criteria, maybe not others. Instead of wringing your hands about how terrible it is that this concept cannot be unambiguously defined, have fun with the fuzzy richness of the idea. Try to understand what motivates other people to say there is a bond there or isn’t. Always think about what change (chemical perturbation) you can do to probe your ideas.
download presentation (pdf, 1.8 MB)
Xian Shi, Research Scientist in the pharmaceutical industry (1997 – 2010): Centaur Pharmaceuticals,
Santa Clara, CA; Research Triangle Institute, Research Triangle Park, NC; Exelixis
Pharmaceuticals, South San Francisco, CA
PhD, SUNY-Binghamton, 1996
“Carbon-Carbon Bond Formation by Reductive Couplings with TiCl2, ZrCl2 and HfCl2”
The reagents, TiCl2, ZrCl2, and HfCl2, all readily obtainable by treating the appropriate MCl4 with two equivalents of n-BuLi in THF, can reductively couple a spectrum of carbonyl derivatives, benzylic halides, benzylic alcohols, acetylenes and certain olefins with the formation of carboncarbon bonds. The order of reactivity has been shown as TiCl2 < ZrCl2 < HfCl2 in the dehalogenative dimerizing reactions of benzal chloride and of benzotrichloride. That acetophenone is coupled to produce only racemic-2,3-diphenyl-2,3-butanediol and diphenylacetylene is coupled to yield exclusively (E,E)-1,2,3,4-tetraphenyl-1,3-butadiene is interpreted to mean that the couplings proceed through an oxidative addition involving a concerted two electron transfer (TET) process with the formation of a 1,1-dichlorometalla(IV) cyclopropane intermediate.
download presentation (pdf, 123 KB)
John N. Gitua, Drake University, Des Moines, Iowa
PhD, SUNY-Binghamton, 2005
“Reactions of Unsaturated Organic Substrates with Dialkyltitanium(IV) Complexes: The Epititanation Process”
Dialkyltitanium(IV) derivatives, R2TiE2, where E = X, OR, have been shown to react with unsaturated organic substrates such as olefins, acetylenes, nitriles, aldehydes, ketones and imines, by undergoing in high yield transfer-epititanation. The efficient transfer-epititanation of the pi-bonded organic substrates by R2TiE2 reagents was readily achieved in THF at -78°C to generate three-membered titanacyclopropa(e)nes, which were readily converted into useful metal-free organic derivatives via protolysis/ deuteriolysis or by insertion of an unsaturated monomer into the C-Ti bond. Such insertions in the case of 1-alkenes lead to stereostereoselective polymerizations of 1-alkenes or to cyclotrimerizations of acetylenes yielding aromatic products.
download presentation (pdf, 448 KB)
Renuka N. Manchanayakage, Susquehanna University, Selinsgrove, Pa.
Postdoctoral Research Associate, SUNY-Binghamton, 2008
“Electron-transfer Rearrangements of Dibenzodiazocine Derivatives: Effective Electron Traps for Organometallic Reactions”
The electron-transfer reductions of different dibenzodiazocine derivatives that contain nonplanar eight-membered rings by use of alkali metals in THF have led to profound skeletal rearrangements. These diazocines can also readily capture an electron from various active organometallics of lithium or magnesium to initiate SET reductions. Therefore, these diazocines may prove to be most effective electron traps for the detection of single-electron transfer (SET) in such organometallic reactions with organic substrates.
download presentation (pdf, 892 KB)
John J. Eisch Binghamton University
Distinguished Professor of Chemistry, Binghamton University
“Retrospect, Prospect, and Gratitude”
download presentation (pdf, 369 KB)