This talk is dedicated to the celebration of Prof. Robert Gilliard’s contributions to the main group inorganic chemistry on the occasion of his 2021 Organometallics Distinguished Author Award. My presentation will focus on the aspects of fundamental chemistry associated with the functionalization and properties of polyhedral boron clusters. Specifically, we have been interested in the generation and reactivity studies of B-centered nucleophiles and radicals associated with these species. During the first half of the talk, I will describe how the nucleophilic and/or radical character of the boron vertices in some of these clusters can be harnessed by using late transition metal chemistry. These observations have guided our development of several synthetic methodologies enabling derivatization of these species in a catalytic fashion via pathways that are reminiscent of cross-coupling chemistry with classical organic substrates. Furthermore, we have recently successfully applied this strategy for bioconjugation transformations with unprotected peptides and proteins. In the second half of the presentation, I will demonstrate how some boron clusters can act as competent nucleophiles without the aid of transition metals. I will highlight some unique features of the nucleophilic character of the small boron clusters that can be applied to carbon-based electrophiles as well as main-group electrophiles (e.g., R<sub>2</sub>PCl, RSeCl) to generate the corresponding borylated species featuring B-C, B-Se and B-P bonding interactions.

Multifaceted reactivity of boron-based vertices in polyhedral boron clusters

ACS Spring 2022

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