Fe-Catalyzed Conversion of N₂ to N(SiMe₃)₃ via an Fe-Hydrazido Resting State

The catalytic conversion of N₂ to N(SiMe₃)₃ by homogeneous transition metal compounds is a rapidly developing field, yet few mechanistic details have been experimentally elucidated for 3 d element catalysts. Herein we show that Fe(PP)₂(N₂) (PP = R₂PCH₂CH₂PR₂; R = Me, 1^Me; R = Et, 1^Et) are highly effective for the catalytic production of N(SiMe₃)₃ from N₂ (using KC₈/Me₃SiCl), with the yields being the highest reported to date for Fe-based catalysts. We propose that N₂ fixation proceeds via electrophilic N_β silylation and 1e^- reduction to form unstable Fe^I(NN-SiMe₃) intermediates, which disproportionate to 1^Me/Et and hydrazido Fe^II[N-N(SiMe₃)₂] species (3^Me/Et); the latter act as resting states on the catalytic cycle. Subsequent 2e^- reduction of 3^Me/Et leads to N-N scission and formation of [N(SiMe₃)₂]^- and putative anionic Fe imido products. These mechanistic results are supported by both experiment and DFT calculations.