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

被引：51

作者：

Piascik, Adam D. ^{[1
]}

Li, Ruohao ^{[1
]}

Wilkinson, Harry J. ^{[1
]}

Green, Jennifer C. ^{[2
]}

Ashley, Andrew E. ^{[1
]}

机构：

[1] Imperial Coll London, Dept Chem, Exhibit Rd, London SW7 2AZ, England

[2] Univ Oxford, Inorgan Chem Lab, South Parks Rd, Oxford OX1 3QR, England

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 34期

基金：

英国工程与自然科学研究理事会;

关键词：

AMBIENT REACTION CONDITIONS; MOLECULAR DINITROGEN; REDUCTION; COMPLEXES; NITROGENASE; FUNCTIONALIZATION; INTERMEDIATE; SILYLATION; SILYLAMINE; MECHANISM;

D O I：

10.1021/jacs.8b06999

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The catalytic conversion of N-2 to N-(SiMe3)(3) by homogeneous transition metal compounds is a rapidly developing field, yet few mechanistic details have been experimentally elucidated for 3d element catalysts. Herein we show that Fe(PP)(2)(N-2) (PP = R2PCH2CH2PR2; R = Me, 1(Me); R = Et, 1(Et)) are highly effective for the catalytic production of N(SiMe3)(3) from N-2 (using KC8/Me3SiCl), with the yields being the highest reported to date for Fe-based catalysts. We propose that N-2 fixation proceeds via electrophilic N-beta 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.

引用

页码：10691 / 10694

页数：4

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