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Research in the Grapperhaus Group focuses on the inorganic/bio-inorganic chemistry of
transition metal-thiolate complexes. In general, we are interested in the electronic
structure of metallothiolates and their reactivity. Our investigations require a combination of
synthesis, reactivity, computation, spectroscopy, and other physical characterizations including
x-ray crystallography and electrochemistry. A synopsis of some current projects is given below.
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Project #1 Non-Innocent Metal-Thiolates
This project focuses on metal-thiolate complexes that undergo ligand-centered oxidations generating metal-coordinated thiyl radicals. The reactivity of organic thiyl radicals with organic compounds can be consolidated into three major categories; disulfide formation, H-atom abstraction, and addition to unsaturated compounds. While oxidation of metal-thiolates to disulfides is well known, and is often suspected as the aerobic decomposition pathway, the other reaction pathways are less well developed. Our research is directed towards systems that support reactive metal-coordinated thiyl radicals with an emphasis on H-atom abstraction and addition of unsaturated compounds.
Students on this project gain experience in synthesis, electrochemical methods, spectroscopy, and/or computational methods.
Current Student: Kagna Ouch
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Project #2 Nitrile Hydratase Mimics
The Nitrile Hydratase (NHase) enzyme contains a unique Fe(III) (or Co(III)) center that features oxygenated cysteine and deprotonated amide ligands. The cysteine oxygenation is crucial for activity. Our interest is focused on the key factors that promote sulfur-centered oxygenation upon air exposure of iron-thiolates and the impact of sulfur-oxygenation of the activity of functional NHase mimics.
Students on this project gain experience in air-free synthesis, ligand-design, reactivity, spectroscopy, electrochemical methods, and/or computational methods.
Current Students: Martin O'Toole, Cesar Masitas
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Other Collaborations
Our group actively collaborates with Prof. Pawel Kozlowski on all computational investigations.
X-ray crystallographic studies are the result of a collaboration with Dr. Mark Mashuta.
The Grapperhaus group also collaborates with Prof. Robert Buchanan on the synthesis and characterization of imidazole-thioalte complexes. These complexes have been prepared as models of nickel-containing superoxide dismutase.
Current Student: Larry Wood
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