Synthesis and reactivity of early transition metal "Frustrated Lewis Pairs"

Date of Award


Degree Type


Degree Name



Chemistry and Biochemistry


Chemistry, Inorganic.

Creative Commons License

Creative Commons Attribution-Noncommercial-No Derivative Works 4.0 License
This work is licensed under a Creative Commons Attribution-Noncommercial-No Derivative Works 4.0 License.


Our research group recently introduced the new concept of "Frustrated Lewis Pairs" (FLP) wherein sterically demanding Lewis acids and bases do not interact in the expected donor-acceptor fashion, but rather exhibit unique reactivity. To date this concept of FLPs has been limited to main group systems. In this thesis we demonstrate that Lewis acidic early metal cations can activate small molecules in the presence of sterically demanding donors to exhibit unique reactivity. The cationic Lewis acids [Cp2Zr(O't'Bu)] +, [Cp2Zr(OPh)]+, [Cp2Zr(OMes)] + and [Cp2Zr(ODipp)]+ are generated by the reaction between the neutral precursor compound and methyl abstracting reagents [Ph3C][B(C6F5)4] and B(C 6F5)3. The reactions of these early metal cations, sterically hindered phosphines with molecular hydrogen and ethylene affords a unique route to early metal hydride species and olefin inserted products. Observed products were generated ' in-situ' and characterized fully by multinuclear 1-D and 2-D NMR spectroscopy.