Fe-Catalyzed Conversion of N 2 to N(SiMe 3 ) 3 via an Fe-Hydrazido Resting State

The catalytic conversion of N to N(SiMe ) 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) (N ) (PP = R PCH CH PR ; R = Me, 1 ; R = Et, 1 ) are highly effecti...

Full description

Saved in:
Bibliographic Details
Published in:Journal of the American Chemical Society 2018-08, Vol.140 (34), p.10691-10694
Main Authors: Piascik, Adam D, Li, Ruohao, Wilkinson, Harry J, Green, Jennifer C, Ashley, Andrew E
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The catalytic conversion of N to N(SiMe ) 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) (N ) (PP = R PCH CH PR ; R = Me, 1 ; R = Et, 1 ) are highly effective for the catalytic production of N(SiMe ) from N (using KC /Me SiCl), with the yields being the highest reported to date for Fe-based catalysts. We propose that N fixation proceeds via electrophilic N silylation and 1e reduction to form unstable Fe (NN-SiMe ) intermediates, which disproportionate to 1 and hydrazido Fe [N-N(SiMe ) ] species (3 ); the latter act as resting states on the catalytic cycle. Subsequent 2e reduction of 3 leads to N-N scission and formation of [N(SiMe ) ] and putative anionic Fe imido products. These mechanistic results are supported by both experiment and DFT calculations.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.8b06999