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

氮分子合成甲硅烷基二氮烷及其作为红色前体的应用研究

• 批准号: 61850149
• 负责人: HIDAI Masanobu
• 金额: $ 2.3万
• 依托单位: University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research
• 财政年份: 1986
• 资助国家: 日本
• 起止时间: 1986 至 1987
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-61850149/
• 关键词: Silyldiazene; Silysiazenido complex; Silylhydrazido complex; 触媒的シリルアミン合成; 窒素錯体; トリメチルシリル化反応; ジアゼニド錯体; ヒドラジド錯体

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.

在苯中用Cf_3SO_3SiMe_3的Me_3SiMe_3处理一系列氮配合物[M(N_2)_22(L)_4](M=W，Mo：L=叔膦)，在温和的条件下生成三甲基硅基二叠氮(MNSiMe_3)和甲硅肼(2-)(MNNHSiMe_3)。前者很好地对应于从分子氮到硅基二叠氮烷的中间阶段，尽管我们还没有成功地将硅基二叠氮基转化为硅基二氮化合物。另一方面，我们最近发现，在顺式-(Mo(N_2)_2)_2(Pme_2Ph)_4存在下，如果在30゜℃的常压N_2气氛下用Na弥散处理Me_3SiCl得到N(SiM_(13)N_2)_3和HN(SiMe_3)_2。硅胺的形成是催化的，目前观察到的最高产率为38%(以Me&lt；23&gt；SiCl2为基准)，相当于以钼为基准的25个转化率。在相同的反应条件下，钨类似物的催化活性远低于钼络合物。

项目成果

Masanobu Hidai: "Reactions of Coordinated Ligands (in press)" Plenum Press,

Masanobu Hidai：“协调配体的反应（正在印刷中）”全体会议出版社，

Keiko Orisaku: Bull.Chem.Soc.Jpn.

织作惠子：Bull.Chem.Soc.Jpn。

Keiko Orisaku: J.Am.Chem.Soc.

织作惠子：J.Am.Chem.Soc。

千鯛眞信: 科学. 57. 157-163 (1987)

仙台正信：《科学》。 57. 157-163 (1987)

Masanobu Hidai: "Molybdenum Enzymes" John Wiley & Sons,Inc., 56 (1985)

Masanobu Hidai：“钼酶”约翰·威利