CURRENT PROJECTS

Hydrogen Atom Transfer:

Elizabeth has been examining hydrogen atom transfer from tris(diimine) metal complexes to the stable nitroxide, TEMPO.  Hydrogen atom transfer reactions are usually associated with negligible changes in the ground-state entropy.  These systems, however, show a large ground-state entropy change, DSo = -30 +/- 2 cal mol-1
K-1.  She has been examining the molecular origins of this unusual entropy." 

Todd studies concerted proton-electron transfer (CPET) in the oxidation of small molecule phenol-base compounds where intermolecular electron transfer is coupled to intramolecular proton transfer.  These reactions serve as a model for biological proton-coupled electron transfer processes involving tyrosine residues, such as the oxidation of Tyrz cofactor in Photosystem II.  Of particular interest is the effect of the proton transfer on the kinetics and thermodynamics of the overall CPET process. His work includes organic synthesis, ab initio calculations, thermodynamic measurements and the determination of reaction rates.

Adam is studying concerted proton-coupled electron transfer (CPET) reactions with ruthenium acetylacetonato pyridine-imidazole complexes.

Chris is investigating the reactivity of oxovanadium compounds, especially their ability to act as hydrogen atom acceptors or donors.  More specifically, aerobic oxidation of oxohydroxovanadium(IV) compounds in THF has been found to give the oxoperoxovanadium(V) product quantitatively.  He is also studying the net transfer of a proton and an electron between oxohydroxovanadium(IV) and cis-dioxovanadium(V) compounds, and whether these reactions can be understood using Marcus theory.

Virginia is studying CPET with ruthenium carboxylic acid (substituted) terpyridine complexes, and will also be studying the nonadiabatic effects of CPET with a cobalt bi-imidazoline complex.

Jeff is working on increasing his level of professionalism.  When that doesn't keep him busy, he synthesizes complexes that will be used for CPET studies.

Strong Oxidants and Catalysis:

Takao is investigating alkane oxidation by OsO₄.

Jessica is exploring the reactivity of hydrazines with ruthenium complexes in the interest of catalytic amination reactions of alkenes and alkynes.

Kem previously worked on the OsO₄(L) (L = py, ^tbupy) oxidation of s bonds using R₃M-H substrates (M = Si, R= Et, Ph, ⁱPr, PhMe₂; M= Sn, R= Bu) and boranes (pinacolborane, (CH₃)₄C₂O₂BH and 9-BBN, [(CH₂)₆(CH)₂BH]₂.  She is currently working on the synthesis of novel Ir^V amine complexes.

Lisa is working on the synthesis of Ir^V Cp* complexes.