Publications

BibTex format

@article{Piascik:2018:10.1021/jacs.8b06999,
author = {Piascik, AD and Li, R and Wilkinson, HJ and Green, JC and Ashley, AE},
doi = {10.1021/jacs.8b06999},
journal = {Journal of the American Chemical Society},
pages = {10691--10694},
title = {Fe-catalyzed conversion of N2 to N(SiMe3)3 via an fe-hydrazido resting state},
url = {http://dx.doi.org/10.1021/jacs.8b06999},
volume = {140},
year = {2018}
}

Download

RIS format (EndNote, RefMan)

TY  - JOUR
AB  - 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, 1Me; R = Et, 1Et) 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 Nβ silylation and 1e- reduction to form unstable FeI(NN-SiMe3) intermediates, which disproportionate to 1Me/Et and hydrazido FeII[N-N(SiMe3)2] species (3Me/Et); the latter act as resting states on the catalytic cycle. Subsequent 2e- reduction of 3Me/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.
AU  - Piascik,AD
AU  - Li,R
AU  - Wilkinson,HJ
AU  - Green,JC
AU  - Ashley,AE
DO  - 10.1021/jacs.8b06999
EP  - 10694
PY  - 2018///
SN  - 1520-5126
SP  - 10691
TI  - Fe-catalyzed conversion of N2 to N(SiMe3)3 via an fe-hydrazido resting state
T2  - Journal of the American Chemical Society
UR  - http://dx.doi.org/10.1021/jacs.8b06999
UR  - https://www.ncbi.nlm.nih.gov/pubmed/30114921
UR  - https://pubs.acs.org/doi/10.1021/jacs.8b06999
UR  - http://hdl.handle.net/10044/1/62355
VL  - 140
ER  -

Download

DrAndyAshley

Contact

Location

Summary

Citation

BibTex format

RIS format (EndNote, RefMan)