Imayoshi Ryuji, Tanaka Hiromasa, Matsuo Yuki, Yuki Masahiro, Nakajima Kazunari, Yoshizawa Kazunari, Nishibayashi Yoshiaki
Institute of Engineering Innovation, The University of Tokyo, Yayoi, Bunkyo-ku, Tokyo 113-8656 (Japan).
ESICB, Kyoto University, Nishikyo-ku, Kyoto 615-8520 (Japan).
Chemistry. 2015 Jun 8;21(24):8905-9. doi: 10.1002/chem.201501088. Epub 2015 May 5.
The first successful example of cobalt-catalyzed reduction of N2 with Me3 SiCl and Na as a reductant, under ambient reaction conditions, gives N(SiMe3 )3 , which can be readily converted into NH3 . In this reaction system, 2,2'-bipyridine (bpy) is found to work as an effective additive to improve substantially the catalytic activity. CoN2 complexes bearing three Me3 Si groups as ancillary ligands are considered to work as key reactive species based on DFT calculations. The DFT results also allow the proposal of a detailed reaction pathway for the transformation of N2 into N(SiMe3 )3 .
在环境反应条件下，以三甲基硅氯（Me3SiCl）和钠作为还原剂，钴催化还原氮气的首个成功实例得到了三（三甲基硅基）胺（N(SiMe3)3），它可以很容易地转化为氨气。在该反应体系中，发现2,2'-联吡啶（bpy）作为一种有效的添加剂能大幅提高催化活性。基于密度泛函理论（DFT）计算，带有三个三甲基硅基作为辅助配体的钴-氮气配合物被认为是关键的反应物种。DFT计算结果还为氮气转化为三（三甲基硅基）胺提出了详细的反应路径。
