Enforced perturbations away from classical geometries can be used to generate unusual frontier molecular orbital manifolds leading to valuable reactivity. For main group compounds, distortion from the VSEPR-predicted structures can be achieved by using multidentate pincer ligands, many of which have been extensively studied in the context of transition metal coordination chemistry.<br/><br/>Our research program focuses on geometric control of chemical properties at molecular and macromolecular length scales. As part of this effort, we have pioneered the molecular chemistry of planar trivalent bismuth centres (cf. the classically pyramidal geometry of such compounds), and demonstrated their geometrically-induced planar Lewis acidity. This talk will reveal our efforts at finely controlling this functional property using a combination of Hammett and Coulomb tuning. It will also reveal some unexpected redox chemistry observed upon varying the ligand backbone, which has consequences for our mechanistic understanding of catalytic reactions involving the Bi(I/III) redox couple.

Exploring flatland at bi: Ligand-controlled lewis acid and redox chemistry at planar trivalent bismuth centres

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ACS Fall 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.