Date of Award

Spring 5-9-2020

Document Type

Honors Thesis



First Advisor

Dr. Bess Vlaisavlijevich

Second Advisor

Dr. Pere Miró

Third Advisor

Dr. James Hoefelmeyer


Cooperative ligand reactivity, triaminoborane-bridged diphosphine, ligands, anions, oligomer ions

Subject Categories

Inorganic Chemistry | Other Chemistry


Reactive ligand platforms containing trisubstituted boranes have been effective in promoting new types of small molecule reactivity and catalysis with transition metals. Our project is aimed at developing triaminoborane-bridged diphosphines that participate in cooperative ligand-centered reactivity while bound to transitions metals. Here we present a density functional theory (DFT) mechanistic study on a series of ligand centered reactions at a boron center on a metal complex, PhTBDPhosMCl2 (M = Ni or Pd and TBDPhos = 1,8,10,9-triazaboradecalin). Our work focuses specifically on the nickel complexes. PhTBDPhosNiCl2 can react with several molecules to produce trans H-X addition (X=OH or F) across the bridgehead N-B bond. In the presence of counterion (e.g. OTf-, Ntf-) PhTBDPhosNiCl2 forms dimers. For select cases, the reaction mechanism was computed. We are also broadly interested in the effect changing the size of the R groups on the phosphorus in the ligand has on the reactivity of (RTBDPhos)Ni(Ln‑) species. Our results suggest that a labile chloride ligand plays an important role in the observed reactivity and that thermodynamics drive product formation. To further understand this, we have studied additional complexes where either the chloride ligands are replaced with stronger coordinating ligands or the substituents on the ligand itself are modified.



To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.