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College of Arts and Sciences

Department of Chemistry

Chemistry Research: William Geiger

William E. Geiger

Geiger photo

William E. Geiger, Ph.D., Research-Active Emeritus Professor of Chemistry

  • Ph.D., Cornell University, Ithaca, NY 1969
  • postdoctoral fellowship, Northwestern University, 1969-1970
  • Assistant Professor of Chemistry, Southern Illinois University, Carbondale, IL, 1970-74
  • Assistant Professor of Chemistry, University of Vermont, 1974-77
  • Associate Professor of Chemistry, University of Vermont, 1977-82
  • Professor of Chemistry, University of Vermont, 1982-2011
  • Pomeroy Professor of Chemistry, University of Vermont, 1997-2011
  • Emeritus Professor of Chemistry, University of Vermont, 2011
  • University of Vermont University Scholar, 1984
  • Member, Vermont Academy of Science and Engineering, 2009
  • Curriculum vitae
Area of expertise

analytical chemistry, inorganic chemistry, electrochemistry

Contact Information

Email: William.Geiger@uvm.edu

Phone: (802) 656-0268

Office: Cook Rm A221

Research

An electron is the simplest chemical reagent. Chemists have increasingly recognized the role of electron-transfer reactions in the laboratory and in nature. Our research focuses on the electron-transfer properties of transition-metal containing complexes, with the primary aim of understanding how the structure and reactivity of the complex is changed by addition or removal of electrons.

Many important chemical transformations can be initiated electrochemically or modeled by electrode processes. In doing so we can often uncover fundamentally important aspects of reactions that are inaccessible through ordinary reaction chemistry.

We use a variety of physical methods to address these problems, including voltammetry experiments that can observe intermediates with lifetimes as short as 10 µs. Many of our electrochemical experiments are interfaced with spectroscopic instruments that enable us to use magnetic resonance spectroscopies, optical spectroscopy (including the near-IR region) and infrared spectroscopy to characterize electron-transfer products. A significant aspect of our research involves the development of fiber-optic technologies to better interface the IR region with electrochemical methods.

Our present research involves molecules and electron-transfer reactions which are important in homogeneous catalysis, molecular wires, or battery technologies.

Selected Publications

Nafady, A.; Costa, P.J.; Calhorda, M.J.; Geiger, W.E. "Electrochemical Oxidation of CoCp(CO)2: Radical-Substrate Reaction of a 17e-/18e- Pair and Production of a Unique Dimer Radical" J. Am. Chem. Soc. 2006, 128, 16587.

Barriére, F.; Geiger, W.E. "Use of Weakly-Coordinating Anions to Develop an Integrated Approach to the Tuning of Delta E½ Values by Medium Effects" J. Am. Chem. Soc. 2006, 128, 3980.

Chong, D.; Nafady, A.; Costa, P.J.; Calhorda, M.J.; Geiger, W.E. "Anodic Preparation of [Re2Cp2(CO)6]2+: a Dimeric Dication that Provides the Powerful One-electron Oxidant [ReCp(CO)3]+" J. Am. Chem. Soc. 2005, 127, 15676.

Stoll, M.; Geiger, W. E. (et al.) "Stepwise Hapticity Changes in Sequential One-Electron Redox Reactions of Indenyl-Mo Complexes," J. Am. Chem. Soc. 2001, 123, 10595.

LeSuer, R. J.; Geiger, W. E. "Improved Electrochemistry in Low-Polarity Media Using Tetrakis(penta-fluorophenyl)borate Salts as Supporting Electrolytes," Angew. Chem. Int. Ed. Engl. 2000, 39, 248.

Last modified September 20 2013 10:26 AM

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