From Carbene-Dithiolene Zwitterion Mediated B-H Bond Activation to BH3·SMe2-Assisted Boron-Boron Bond Formation.

ABSTRACT

The 11 reaction of the carbene-stabilized dithiolene zwitterion 1 with BH3·SMe2 gave the dithiolene-based hydroborane 2 and the doubly hydrogen-capped CAAC species 3 via hydride-coupled reverse electron transfer processes. The mechanism of this transformation was probed computationally using density functional theory. The subsequent 21 reaction of 2 with 1 resulted in 4 and 3, suggesting that 1 can mediate the B-H bond activation not only for BH3 but also for monohydroboranes. In the presence of BH3·SMe2, 2 was unexpectedly converted to the corresponding diborane(4) complex 5 through a dehydrocoupling reaction at an elevated temperature.