Group 6 Transition-Metal/Boron Frustrated Lewis Pair Templates Activate N and Allow its Facile Borylation and Silylation.

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.