氯过甲基环六硅烷Si 6 Me 12- n Cl n(1 ; n = 1),1,3-Cl 2 Si 6 Me 10和1,4-Cl 2 Si 6 Me 10(分别为2和3 ; n = 2)和分别具有NH 3或NaNH 2的1,3,5-Cl 3 Si 6 Me 9(4 ; n = 3),得到相应的氨基衍生物Si 6 Me12- Ñ(NH 2)Ñ(5 - 8),这是令人惊讶的朝向在纯态自缩合稳定。在NH的痕迹的存在4氯,工作作为酸催化剂,5 - 8慢慢分解用NH的损失3,得到仍含有完整cyclohexasilanyl部分聚硅氮烷。在1,4-二氨基十甲基甲基环己硅烷(7)的情况下,分子内缩合产物9与一些聚合材料一起形成。X射线结构分析9,它是第一个在结构上表征的7-氮杂六硅基or烷硼烷,在船型中具有环烷硅烷环的降冰片烷样结构。氨基二十碳六环硅烷(5)容易被n- BuLi质子化,得到预期的氨基酰胺锂LiHNSi
Mercury-sensitized photolysis of Me2SiH2 The disproportionation reactions of the Me2SiH radical
作者:C. Kerst、P. Potzinger
DOI:10.1039/a605762d
日期:——
Mercury-sensitized photolysis of Me
2
SiH
2
yields in the primary step an Me
2
HSi radical and an H atom
with a quantum yield of one. The Me
2
HSi radicals undergo a
combination reaction [k(2)] as well as two kinds of
disproportionation reactions leading to dimethylsilylene
[k(3)] and 1-methylsilaethene [k(4)]. The following
branching ratios have been determined:
k(3)/[k(2)+k(3)+k(4)]=0.64
±0.10 and
k(4)/[k(2)+k(3)+k(4)]0.007.
For Me
3
Si radicals the branching ratio for
disproportionation was also determined and a value of 0.063 was
obtained.
Me 2 SiH 2 的汞敏化光解第一步产生一个 Me 2 HSi 自由基和一个 H 原子,量子产率为 1。Me 2 HSi 自由基会发生一个结合反应[k(2)]以及两种歧化反应,最终生成二甲基硅烷基[k(3)]和 1-甲基硅烷基[k(4)]。测定的支化率如下:k(3)/[k(2)+k(3)+k(4)]=0.64 ±0.10,k(4)/[k(2)+k(3)+k(4)]0.007。对于 Me 3 Si 自由基,还测定了歧化支化率,结果为 0.063。
�ber ?,?-�bergangsmetallsubstituierte Oligosilane
作者:E. Hengge、M. Eibl、B. Stadelmann
DOI:10.1007/bf00819520
日期:1993.5
Methyloligosilanes with n = 3, 4, 5 and 6 with dicarbonyl-cyclopentadienyl-iron- and tricarbonyl-triphenylphosphane-cobalt-groups in terminal positions were synthesized for the first time and characterized by NMR, IR, and MS. The NMR spectra were discussed in detail.
Hydrogen‐Bridged Oligosilanylsilyl Mono‐ and Oligosilanylsilyl Dications
作者:Jelte P. Nimoth、Thomas Müller
DOI:10.1002/chem.202104318
日期:2022.2.16
The presence of multiple Si−H functionalities in one molecule is used to generate at low temperatures oligosilane-based mono- and dications that are stabilized by intramolecular 3c2e Si−H−Si bridges. For the oligosilanylsilyl monocation, a rapid intramolecular Si−H group exchange is monitored by NMR spectroscopy at low temperatures. This dynamic process is not observed for the corresponding dication
with some polymeric material. The X-ray structure analysis of 9, which is the first structurally characterized 7-azahexasilanorbornane, exhibits a norbornane-like structure with the cyclohexasilane ring in a boat conformation. Aminoundecamethylcyclohexasilane (5) is easily deprotonated by n-BuLi to give the expected lithium amide LiHNSi6Me11. With NaNH2, however, the open-chain ringscission product
氯过甲基环六硅烷Si 6 Me 12- n Cl n(1 ; n = 1),1,3-Cl 2 Si 6 Me 10和1,4-Cl 2 Si 6 Me 10(分别为2和3 ; n = 2)和分别具有NH 3或NaNH 2的1,3,5-Cl 3 Si 6 Me 9(4 ; n = 3),得到相应的氨基衍生物Si 6 Me12- Ñ(NH 2)Ñ(5 - 8),这是令人惊讶的朝向在纯态自缩合稳定。在NH的痕迹的存在4氯,工作作为酸催化剂,5 - 8慢慢分解用NH的损失3,得到仍含有完整cyclohexasilanyl部分聚硅氮烷。在1,4-二氨基十甲基甲基环己硅烷(7)的情况下,分子内缩合产物9与一些聚合材料一起形成。X射线结构分析9,它是第一个在结构上表征的7-氮杂六硅基or烷硼烷,在船型中具有环烷硅烷环的降冰片烷样结构。氨基二十碳六环硅烷(5)容易被n- BuLi质子化,得到预期的氨基酰胺锂LiHNSi