Date of Award
Dr. Bess Vlaisavlijevich
Dr. Pere Miró
Dr. James Hoefelmeyer
Cooperative ligand reactivity, triaminoborane-bridged diphosphine, ligands, anions, oligomer ions
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.
Kirkvold, Clara, "Mechanistic Study of Cooperative Ligand-Centered Reactivity in Triaminoborane-Bridged Diphosphine Complexes" (2020). Honors Thesis. 96.