Group6 Transition-Metal/Boron Frustrated Lewis Pair Templates Activate N2 and Allow its Facile Borylation and Silylation

The reaction of trans-[M(N-2)(2)(dppe)(2)] (M=Mo, 1(Mo), M=W, 1(W)) with B(C6F5)(3) (2) provides the adducts [(dppe)(2)M=N=N-B(C6F5)(3)] (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-2 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.