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Title

Ligand-Centered Reactivity in Triaminoborane-Bridged Diphosphine Complexes

Document Type

Poster

Publication Date

5-2020

Disciplines

Chemistry

Abstract

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) study on a series of ligand centered reactions at a borenium center on a metal complex, Ph(TBDPhos)MCl2 (M=Ni). Ph(TBD)PhosNiCl2 will react with several molecules to produce trans H-X addition on the bridgehead N-B bond. In the presence of counter-anion (e.g. OTF-, Ntf-) to form dimers. For select cases, the reaction mechanism was computed. We are broadly interested in the effect changing the metal (Ni, Pd, Pt), changing the ligand, and changing the size of the R groups on the phosphorus in the ligand has on the reactivity of (RTBDPhos)M(Ln) species. Our results suggest that a labile chlorine 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 chlorine ligands are replaced with stronger coordinating ligands or the substituents on the ligand itself are modified.

First Advisor

Bess Vlaisavljevich

Research Area

Chemistry

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