Redox-Active Boron Clusters.

ConspectusIn this Account, we discuss our group's research over the past decade on a class of functionalized boron clusters with tunable chemical and physical properties, with an emphasis on accessing and controlling their redox behavior. These clusters can be thought of as three-dimensional aromatic systems that have distinct redox behavior and photophysical properties compared to their two-dimensional organic counterparts. Specifically, our lab has studied the highly tunable, multielectron redox behavior of B(OR) clusters and applied these molecules in various settings.

Vertex Differentiation Strategy for Tuning the Physical Properties of -Dodecaborate Weakly Coordinating Anions.

We report the synthesis and characterization of various compounds containing the 1,7,9-hydroxylated -dodecahydrododecaborate (BH(OH)) cluster motif. Specifically, we show how the parent compound can be synthesized on the multigram scale and further perhalogenated, leading to a new class of vertex-differentiated weakly coordinating anions. We show that a postmodification of the hydroxyl groups by alkylation affords further opportunities for tailoring these anions' stability, steric bulk, and solubility properties.

Arene C-H borylation strategy enabled by a non-classical boron cluster-based electrophile.

Introducing a tri-coordinate boron-based functional group (e.g., boronic ester) into an unactivated C-H bond in the absence of directing groups is an ongoing challenge in synthetic chemistry.