No abstract

Set Me3SiH free! The strong Lewis acid B(C6F5)3 catalyzes the release of hydrosilanes from 3‐silylated cyclohexa‐1,4‐dienes with concomitant formation of benzene. Subsequent B(C6F5)3‐catalyzed SiH bond activation allows for alkene hydrosilylation (see scheme). The net reaction is an ionic transfer hydrosilylation. The new technique is particularly attractive in the case of otherwise gaseous, highly flammable hydrosilanes.

The reaction of trans-[M(N ) (dppe) ] (M=Mo, 1 , M=W, 1 ) with B(C F ) (2) provides the adducts [(dppe) M=N=N-B(C F ) ] (3) which can be regarded as M/B transition-metal frustrated Lewis pair (TMFLP) templates activating dinitrogen. Easy borylation and silylation of the activated dinitrogen ligands in complexes 3 with a hydroborane and hydrosilane occur by splitting of the B-H and Si-H bonds between the N moiety and the perfluoroaryl borane. This reactivity of 3 is reminiscent of conventional frustrated Lewis pair chemistry and constitutes an unprecedented approach for the functionalization of dinitrogen.