Study on the syntheses of Silyldiazanes from Molecular Nitrogen and the Application of Silydiazenes as Redical Precursors

在苯中处理CF_3SO_3SiMe_3中的Me_3SiI时，一系列二硝基复合体（M（N_2）_22（L）_4） （M = W， Mo： L =三磷酸酶）有分量的三甲基二甲基以前的compiexes很好地纠正了从分子硝基到硅二氮的中间阶段，但我们还没有成功地在硅二氮组的转换中进行转换。在其他方面，我们最近发现了对Me_3SiCl的钠分散处理，如果THF在30 ° c下N_2给予N（SiMen 13 n2）_3和HN（SiMe_3）_2在顺式存在-（Mo（N_2）_2（PMe_2Ph）_4）。硅胺的形成是催化的，最大值现在被观察到的是38%基于Me_<23>SiCl聊天，而对应的是基于molybdenum的25个转弯数。Tungsten模拟的催化活性比相同反应条件下的分子复合物要低很多。

When treated with Me_3 SiI of CF_3SO_3SiMe_3 in benzene, a series of dinitrogen complexes (M(N_2)_22(L)_4) (M = W, Mo: L = tertiary phosphine) afforded trimethlsilyldiazenido (MNNSiME_3) andteimethylsilyihydrazido(2-) (MNNHSiMe_3) complexes under mild conditions. The former compiexes well correspond to the intermediate stage from molecular nitrogen toward silyldiazanes, although we have not yet succeeded in the conversion of the silyldiasinido groups into silyldiazenes. On the other hand, we have recently found that treatment of Me_3SiCl with Na dispersion if THF at 30゜c under atmospheric pressure of N_2 gives N(SiMen13n2)_3 and HN(SiMe_3)_2 in the presence of cis-(Mo(N_2)_2(PMe_2Ph)_4). The formation of silylamines is catalytic and the maximum yield observed till now is 38% based on Me_<23>SiCl chatged, which correspones to the turnover number of 25 based on the molybdenum. The catalytic activity of the tungsten analogue was much lower than that of the molybdenum complex under the same reaction conditions.