Abstract: | The reaction of trans ‐[M(N2)2(dppe)2] (M=Mo, 1Mo , M=W, 1W ) with B(C6F5)3 ( 2 ) provides the adducts [(dppe)2M=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 N2 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. |