Protonation of Coordinated Dinitrogen Using Protons Generated from Molecular Hydrogen

A new strategy has been developed to synthesize N–H bonds from coordinated N 2 in trans ‐[W(dppe) 2 (N 2 ) 2 ] ( 1 ) using protons generated from H 2 in the presence of (C 6 F 5 ) 3 B and 2,2,6,6‐tetramethylpiperidine, under normal experimental conditions or upon sonication. The complexes [(dppe) 2 WH(NNH 2 )][HB(C 6 F 5 ) 3 ] ( 2 ) and [FW(dppe) 2 (NNH 2 )][HB(C 6 F 5 ) 3 ] ( 3 ) have been successfully isolated and characterized using standard analytical and spectroscopic methods. We have also monitored the progress of the reaction of complex 1 with a frustrated Lewis pair dihydrogen adduct (FLP‐H 2 ) using standard spectroscopic techniques by following the signatures of the reactants and the products. The results of the current studies are promising for fixing N 2 into ammonia by using H 2 , under normal experimental conditions, in the near future.