Directed Synthesis and Chemistry of Unsymmetric Dicationic Diboranes and Their Use in Frustrated Lewis Pair-like Chemistry.

The chemistry of dicationic diboranes with two B atoms that are engaged in direct B-B bonding is by enlarge unexplored, although these molecules have intriguing properties due to their combined Lewis acidic and electron-donor properties. Unsymmetric dicationic diboranes are extremely rare, but especially attractive due to their polarized B-B bond. In this work we report the directed synthesis of several stable unsymmetric dicationic diboranes by reaction between the electron-rich ditriflato-diborane B (hpp) (OTf) (hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-α]pyrimidinate) and phosphino-pyridines, establishing B-N and B-P bonds with the diborane concomitant with triflate elimination. In the case of 2-((ditertbutylphosphino)methyl)pyridine, the B-N bond is formed instantly, but the B-P bond formation requires (due to steric constraints) several days at ambient conditions for completion, creating an intermediate that could be used for frustrated Lewis pair (FLP)-like chemistry. Here we test its reaction with an aldehyde, and propose a new type of FLP-like chemistry.