19th Biannual: John Eisch Lectureship In
Inorganic/Organometallic Chemistry
Friday, April 25, 2025
4 P.M.
Smart Energy Building, Fountain Room
Professor T. Don Tilley
University of California at Berkeley and Lawrence Berkeley National
Laboratory Department of Chemistry
Oxo Metal Clusters in Water Splitting and Bond Activations
The conversion of solar energy into a useful chemical fuel represents a major goal in the drive towards a society fully powered by renewable energy. Several potential fuels are of interest, including hydrogen from proton reduction, and various hydrocarbons from carbon dioxide reduction. To achieve meaningful rates of fuel production, the potential reduction reactions must be coupled to an oxidative reaction that generates electrons and protons. The most reasonable candidate to provide these electrons and protons is water, which can be chemically decomposed to 4 protons, 4 electrons, and oxygen (the oxygen evolution reaction, OER). For solar fuel applications, this water-splitting half reaction must be catalyzed to make it energetically efficient, as accomplished in nature's photosynthesis by a tetra-manganese oxo cluster (the oxygen-evolving complex, OEC). Indeed, related transition-metal oxo cubane clusters represent intriguing model systems and catalyst design motifs for development of new water-splitting catalysts based on the most abundant metals. Molecularly derived catalysts of this type offer a number of potential advantages, including the synthetic tunability of structure-activity relationships and chemical properties. Also, the study of model, high-valent molecular species can provide key insights into the mechanism of water oxidation, and thereby help bridge the gap between solid-state and molecular systems to allow for more rational design of catalysts. This presentation will describe high valent tetracobalt oxo cubane clusters, and the experimental determination of a well-defined mechanism for cubane-catalyzed oxygen evolution via water oxidation. The systematic variation of electronic properties for these clusters, and strategies for their stabilization, will be described. The synthesis and study of clusters doped by another transition metal, and linked bis-cubane complexes, are further topics to be discussed.
- Information about Professor T. Don Tilley
T. Don Tilley received his B.S. degree in chemistry from the University of Texas in 1977 and then went to the University of California at Berkeley where he completed graduate studies (Ph.D. 1982) in organolanthanide chemistry under the direction of Richard Andersen. After his graduate work at Berkeley, he was appointed as an NSF-sponsored exchange postdoctoral fellow to work jointly with Bob Grubbs and John Bercaw at the California Institute of Technology (1981-2) and with Luigi Venanzi and Piero Pino at the ETH in Z眉rich (1982-3). During this period, he developed the chemistry of the (pentamethylcyclopentadienyl)ruthenium fragment. In 1983 he began his independent research career as an Assistant Professor at the University of California at San Diego. There he was promoted to Associate Professor in 1988, and then to Professor in 1990. In 1994, he accepted appointments as Professor of Chemistry at the University of California at Berkeley and as Faculty Senior Scientist at the Lawrence Berkeley National Laboratory. In 2020, he was appointed as the PMP Tech Chancellor's Chair in Chemistry at UC Berkeley.
Tilley has received several recognitions, including an Alfred P. Sloan Fellowship (1988), a Union Carbide Innovation Recognition Award (1991-92), an Alexander von Humboldt Award for Senior Scientists (1998), election to the American Association for the Advancement of Science (1998), the ACS award in Organometallic Chemistry (2002), the Wacker Silicon Award (2003), the Centenary Lectureship and Medal of the Royal Society (2007-8), the ACS Frederic Stanley Kipping Award in Silicon Chemistry (2008), and the ACS Award for Distinguished Service in the Advancement of Inorganic Chemistry (2014). Tilley was elected Chair of the Division of Inorganic Chemistry of the ACS for 2003 and was named a Miller Research Professor for 2004-5. In 2013, he was elected as a Fellow of the American Academy of Arts and Sciences and in 2014 he was named an ACS Fellow. In 2023, he was elected to the National Academy of Sciences. From 2005-2021, Tilley served as the North American Associate Editor for Chemical Communications, covering Inorganic, Organometallic and Materials Chemistry. He has published over 510 papers and has been invited to present 32 named lectures.
- Information about Professor John J. Eisch
John Joseph Eisch joined the Department of Chemistry at 黑料视频 in 1972, as chair and professor of chemistry, with the mandate of fostering the national reputation of its graduate teaching and research. Over the next six years as chair, he guided the recruiting of six senior and junior faculty with this goal in mind, while expanding his own research in organometallic chemistry to a yearly group of eight to 12 graduate and postdoctoral students, with support from federal and industrial resources. In 1983, his composite achievements were recognized by his promotion to the SUNY-wide rank of distinguished professor of chemistry. Further recruiting, notably during the chair tenure of professors Eugene Stevens, Alistair Lees, Wayne Jones and currently, Eriks Rozners, expanded the scope of advanced research into areas of immediate importance, such as nano materials, homogeneous catalysis, analytical sensors, biological transformations and energy storage.
Eisch received the BS degree in chemistry, summa cum laude, from Marquette University in 1952; earned the PhD degree in 1956, with Henry Gilman, at Iowa State University; and served as Union Carbide Research Fellow with Karl Ziegler at the Max-Planck-Institut fu虉r Kohlenforschung, Mu虉lheim, Germany (1956鈥57). After junior professional appointments at St. Louis University and the University of Michigan, he became ordinary professor and department head at the Catholic University of America (1963鈥1972). He retired from his professorial career of 57 years in 2014, the latter 42 years of which were spent at 黑料视频.
The Eisch Group initially had concentrated on the preparation and organic synthetic uses of organometallic reagents of Li, Na, Mg, B and Al, but we were struck by the lack of definitive molecular mechanistic studies in previous work. In ensuing research encompassing reaction kinetics, trapping of any intermediates, IR, UV and X-ray crystallographic measurements, both heterolytic and homolytic C-M cleavages could be involved, as well as 4-centertrapesoidal transition states. Reviews are available in a) 鈥淔ifty Years of Ziegler- Natta Polymerization: From Serendipity to Science,鈥 Organometallics, 2012, 31, 4917鈥4932 and b) Dalton Transactions, (DOI: 10:1039/c4dt010362) 鈥淓mergence of Electrophilic Alumination as the Counterpart of Established Nucleophilic Lithiation.鈥 The original seven articles dealing with the reactions of RLi with the azomethyne groups have been recently published by the Eisch and the Rheingold Crystallographic Group in the European Journal of Organic Chemistry.
Over the years, the research involved the fruitful collaboration of more than 200 students as master鈥檚, doctoral, postdoctoral or baccalaureate associates. The results have been reported in more than 410 scientific publications, in some 280 invited lectures worldwide, in the monograph 鈥淭he Chemistry of Organometallic Compounds鈥 (Macmillian, 1967) and in the edited series, 鈥淥rganometallic Syntheses鈥 (four volumes, J. J. Eisch and R. B. King, authors and editors). He has been an industrial consultant on organometallic chemistry and an expert witness in several patent litigations on Ziegler-Natta polymerization catalysis.
One of the significant discoveries of our studies is that the reaction of organic carbanionic reagents is not a one-step nucleophilic C alpha attack (i) but a two-step electrontransfer and electron-coupling process (ii)(iii).
- Previous Lectureship Recipients
2012
Stephen L. Buchwald - MIT
鈥淧alladium-Catalyzed CarbonNitrogen and Carbon-Carbon Bond-Forming Reactions: Progress, Applications and Mechanistic Studies鈥
2013
David W. C. MacMillan - Princeton University
鈥淭he Use of Photoredox Catalysis in New Organic Bond Forming Reactions鈥
2014
Brian M. Stoltz - California Institute of Technology
鈥淐omplex Natural Products as a Driving Force for Discovery in Organic Chemistry鈥
2015
Eric N. Jacobsen - Harvard University
鈥淎nion-Binding Catalysis鈥
2016
Bob Crabtree - Yale University
鈥淥rganometallic Catalysis for Solar Fuels and Storage鈥Phil S. Baran - The Scripps Research Institute
鈥淭ranslational Chemistry鈥
2017
Stephen J. Lippard - MIT
鈥淯nderstanding and Improving Platinum Anticancer Drugs鈥Daniel A. Singleton - Texas A&M Uniersity
鈥淒ynamic Effects and Energy Labeling in Free-Radical Reactions鈥
2018
Clifford P. Kubiak - University of California, San Diego
鈥淚f You Make a Solar Fuel From CO2, What Should It Be?鈥Scott E. Denmark - University of Illinois at Urbana-Champaign
"Lewis-base Activation of Lewis Acids: An Evolving Paradigm for Catalysis in Main Group Chemistry"
2019
Professor Gregory C. Fu - California Institute of Technology "Nucleophilic Substitution Reactions: A Radical Alternative to SN1 and SN2 Reactions"
John F. Hartwig - University of California, Berkeley
"Selective, Catalytic Functionalization of C-H Bonds with Small and Large Catalysts"
2021
Professor Vern L. Schramm - Albert Einstein College of Medicine
"Enzymatic Transition States and Transition State Analogues"
2022
Karen Goldberg - University of Pennsylvania
"Molecular Oxygen as a Reagent in Late Transition Metal Organometallic Chemistry"
2023
Kendall N. Houk - University of California, Los Angeles "Pericyclic Reactions: Theory, Mechanisms, Dynamics and Role in Biology"
Polly L. Arnold - University of California, Berkeley
"F-Block Dinitrogen Chemistry; from Rarity to Catalysis in a Few Simple Steps"
2024
Professor Gregory H. Robinson - University of Georgia
"N-Heterocyclic Carbenes and Dithiolene Radicals: Counterintuitive Main Group Chemistry"
2025
Professor Melanie Sanford - Moses Gomberg Distinguished University Professor of Chemistry and Arthur F. Thurnau Professor Department of Chemistry University of Michigan
"Development of Metal-Catalyzed Reactions for Introducing Fluorine Into Organic Molecules"Dr. T. Don Tilley - University of California at Berkeley and Lawrence Berkeley National Laboratory Department of Chemistry
"Oxo Metal Clusters in Water Splitting and Bond Activations"