Research Interests
At the University of Saskatchewan
At Oklahoma State University
I started my graduate studies synthesizing branched fluoro-oligogermanes. In the course of this project, I came across germanium cations (germyliums). I studied their immense Lewis acidity, and could apply them in hydrodefluorination (HDF) reactions. Below, you can find summaries of some results from my projects.
• Synthesis of the Elusive Branched Fluoro-oligogermane (Ph3Ge)3GeF
Our group was successful in making (Ph3Ge)3GeX (X=Cl, Br, I) compounds (Organometallics 2011, 30, 5, 1046–1058) but making the fluoride analogue proved to be harder. After several attempts, the key was found to be taking advantage of the extreme Lewis acidity of the germylium intermediate. Typically considered a weakly-coordinating anion (WCA), BF4- acted as an in situ fluoride source. Along with the anionic digermyne fluoride adduct made by Power et al. (J. Am. Chem. Soc. 2010, 132, 38, 13150–13151), (Ph3Ge)3GeF is one of the only fully characterized compounds with both Ge–Ge and Ge–F bonds.
Publication: Organometallics 2018, 37, 12, 1852–1859. [Link]
• HDF of Acid Fluorides and Organofluorines by Ph3GeH
Our continuing efforts for isolating the germylium intermediate led us to examine the capability of the simpler germylium Ph3Ge+ in C–F bond activation. We have been able to show that Ph3GeH with catalytic amounts of [CPh3][B(C6F5)4] can do HDF with acyl fluorides and organofluorines. This approach is simple and mild and can be carried out in neat conditions, with no over-reduction of acyl fluorides or partial HDF of organofluorines.
My favorite part of this project is that several initial reactions were done by 10 high school students at the University of Detroit Jesuit High School (Detroit, MI). These students are included as co-authors. This article was also featured as the cover art for the issue.
Publication: Chemical Communications 2019, 55, 73, 10852–10855. [Link]
• Direct Amidation of Acid Fluorides by Ph3GeNMe2
I attempted many times to get a crystal structure of different germyliums. Germanium amides are compounds that our group used extensively for hydrogermylation reactions. The structure and the memory of working with germyliums led me to think: what if “germanium amides are masked germyliums”? (Turned out not to be true.)
I was able to show that Ph3GeNMe2 can do direct amidation of acid fluorides. This reaction is mild, clean, and has quantitative yields. Our computational studies revealed that the masked germylium pathway is not energetically favorable — instead, the reaction proceeds through a concerted, σ-bond metathesis mechanism.
Publication: Dalton Transactions 2021, 50, 4490–4493. [Link]