Air-Stable Boranes and Borinanes Encapsulated in Organogels for Anionic Ring-Opening (Co)Polymerization.

Organoborane reagents play a pivotal role as Lewis acids in acid-base pairs used in anionic polymerization and in other reactions; yet their high sensitivity to oxygen and moisture necessitates effective stabilization to prevent their oxidation and thus maintain their catalytic activity. In this study, we present novel encapsulation methods employing a cost-effective hexatriacontane (CH, C36) organogel to stabilize sensitive organoborane reagents, including triethyl borane (TEB) and a borinane-based ammonium salt (BNBr). These organoboranes encapsulated in stable, self-standing organogel blocks enable their safe handling in open laboratory environments without the need for a glovebox. Upon heating such borane-containing organogel blocks organoboranes could be freed from the organogel and used to mediate both the homopolymerization of propylene oxide (PO) and the copolymerization of PO with CO. Furthermore, efficient recovery of the C36 gelator from polymerization mixtures is achieved, with mass recovery ranging from 70 % to 90 %. This encapsulation method offers a practical and efficient solution for stabilizing, storing, and handling highly reactive organoborane reagents, thereby broadening their applicability and utilization in various chemical transformations.