An Intramolecular Silylene Borane Capable of Facile Activation of Small Molecules, Including Metal-Free Dehydrogenation of Water.

The first single-component N-heterocyclic silylene borane 1 (LSi-R-BMes ; L=PhC(N Bu) ; R=1,12-xanthendiyl spacer; Mes=2,4,6-Me C H ), acting as a frustrated Lewis pair (FLP) in small-molecule activation, can be synthesized in 65 % yields. Its HOMO is largely localized at the silicon(II) atom and the LUMO has mainly boron 2p character. In small-molecule activation 1 allows access to the intramolecular silanone-borane 3 featuring a Si=O→B interaction through reaction with O , N O, or CO , and formation of silanethione borane 4 from reaction with S . The Si center in 1 undergoes immediate hydrogenation if exposed to H at 1 atm pressure in benzene, affording the silane borane 5-H , L(H )Si-R-BMes . Remarkably, no H activation occurs if the single silylene LSiPh and Mes B intermolecularly separated are exposed to dihydrogen. Unexpectedly, the pre-organized Si-B separation in 1 enables a metal-free dehydrogenation of H O to give the silanone-borane 3 as reactive intermediate.