Group 6 Transition‐Metal/Boron Frustrated Lewis Pair Templates Activate N 2 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(C 6 F 5 ) 3 ( 2 ) provides the adducts [(dppe) 2 M=N=N‐B(C 6 F 5 ) 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.