University of Minnesota
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TOLMAN GROUP LABORATORY

Overview of Research

Current research in the Tolman group encompasses synthetic bioinorganic and organometallic/polymer chemistry. In the bioinorganic area, our objective is to gain a fundamental structural, spectroscopic, and mechanistic understanding of metalloprotein active sites of biological and environmental importance via the synthesis, characterization, and examination of the reactivity of model complexes (Figure 1). The current goal of our research in the organometallic/polymer area is to synthesize and characterize a variety of metal complexes for use as catalysts for the polymerization of cyclic esters. In this project, particular emphasis is being placed on developing and understanding the mechanism(s) of processes for the controlled synthesis of polymers derived from renewable resources (Figure 2).

While the synthesis of new molecules lies at the center of our research effort, we also use a wide array of techniques to characterize the compounds we prepare and to examine their reactivity. Among the characterization methods that we use are X-ray crystallography, NMR, EPR, UV-Vis, FTIR, and resonance Raman spectroscopy, mass spectrometry, GC/MS, and cyclic voltammetry. We also endeavor to unravel reaction mechanisms through kinetics and isotope labeling experiments. Students and postdoctoral associates in the group thus obtain a highly multidisciplinary training in the synthesis, structural and spectroscopic characterization, and mechanistic study of organic, inorganic, and organometallic molecules.

Figure 1. Copper-oxygen complexes that model catalytic intermediates.

Figure 2. Indium catalyst for the heterotactic polymerization of D,L-lactide.


Financial support for the research is provided by the National Institutes of Health, National Science Foundation, and UM Institute for Renewable Energy and the Environment.

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Recent News

*The paper "Catalytic decarbonylation of biomass-derived carboxylic acids as an efficient route to commodity monomers" by Maria O. Miranda, Agostino Pietrangelo, Marc A. Hillmyer, and William B. Tolman has been published online in Green Chemistry (available to institutional journal subscribers in both HTML and PDF formats HERE).--1/5/12
*Welcome to new graduate students Ben Neisen and Gereon Yee, who have joined the group and will work on bioinorganic chemistry projects.--11/23/11
*Two publications in J. Am. Chem. Soc. describing work from the group have appeared online, entitled “X-ray Absorption Spectroscopic and Computational Investigation of a Possible S…S Interaction in the [Cu3S2]3+ Core” and “Rapid C-H Bond Activation by a Monocopper(III)-Hydroxide Complex”. (click for details)
*Dr. Keying Ding joins the group officially on September 12. She worked with Connie Lu's group after receiving her Ph.D. from the University of Rochester, under the tutelage of a Tolman Group alum, Prof. Pat Holland. Welcome Keying!--9/2/11
*Drs. Agostino Pietrangelo, Lei Yang, and Aalo Gupta have left for greener pastures. . .(click for details)--8/16