Thesis Defence: Stabilization of Low-Valent Group XIII Complexes with Polydentate Ligands

Vigneshkumar Pattathil Narayanan, supervised by Dr. Conor Pranckevicius, will defend their thesis titled “Stabilization of Low-Valent Group XIII Complexes with Polydentate Ligands” in partial fulfillment of the requirements for the degree of Master of Science in Chemistry.

An abstract for Vigneshkumar Pattathil Narayanan’s thesis is included below.

Defences are open to all members of the campus community as well as the general public. Registration is not required for in person defences.

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ABSTRACT

A tricyclic 1,4,2-diazaborole was synthesized from a bidentate pyridylcarbene ligand and MesBBr2, and its reduction afforded a novel aromatic boracycle. The nucleophilicity of boron in this species was confirmed via its alkylation with MeI, and a ’Frustrated Lewis Pair’ substrate activation with B(C6F5)3, whereas the reaction with other boranes revealed unprecedented ring expansion reactions to form a diverse family of non-symmetrical 1,4,2,5- diazadiborenes. DFT calculation shed light on the electronic structure of the reduced 1,2,4-diazaborole derivative and provide insight into mechanistic aspects of the observed ring-expansion reactions. Using a tridentate polycyclic CNC pincer ligand, attempts were made to synthesize low-valent aluminium and boron complexes. Even though isolation of a low-valent complexes were unsuccessful, the investigation provided many insights into new synthetic strategies that could potentially be tried in the future to isolate an Al(I) and B(I) complexes. In addition to experimental studies, computational calculations were also performed to evaluate the stability of system and feasibility of further reactions.