排序方式: 共有5条查询结果,搜索用时 31 毫秒
1
1.
Nataliya F. Lazareva Tamara I. Vakul'skaya Alexander I. Albanov Vadim A. Pestunovich 《应用有机金属化学》2006,20(10):696-705
The introduction of the organosilicon substituent into the α‐position of an amino group results in cardinal change of the amine reactivity irrespective of the coordination state of silicon. Amines R2NCH2SiX3 [R = Me, Et, PhCH2, CH2SiX3; SiX3 = SiMe3, Si(OEt)3, Si(OCH2CH2)3N] easily react with AgNO3, to give the corresponding ammonium salts (R2NH+ CH2SiX3)·NO3?. At the same time, Ag(I) is reduced to Ag(0). The interaction of N‐methyl‐N,N‐bis(silatranylmethyl)amine with AgNO3 has been investigated by EPR spectroscopy. It was proven that the reaction involved a single electron transfer stage with the formation of cation radical of this amine. A mechanism of the reaction is proposed. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
2.
Tris(trimethylsilyl)silylamine and the lithiated and silylated Derivatives — X-Ray Structure of the dimeric Lithium Trimethylsilyl-[tris(trimethylsilyl)silyl]amide The ammonolysis of the chlor, brom or trifluormethanesulfonyl tris(trimethylsilyl)silane yields the colorless tris(trimethylsilyl)silylamine, destillable at 51°C and 0.02 Torr. The subsequent lithiation, reaction with chlor trimethylsilane and repeated lithiation lead to the formation of lithium tris(trimethylsilyl)silylamide, trimethylsilyl-[tris(trimethylsilyl)silyl]amine and finally lithium trimethylsilyl-[tris(trimethylsilyl)silyl]amide, which crystallizes in the monoclinic space group P21/n with a = 1 386.7(2); b = 2 040.2(3); c = 1 609.6(2) pm; β = 96.95(1)° and Z = 4 dimeric molecules. The cyclic Li2N2 moiety with Li? N bond distances displays a short transannular Li …? Li contact of 229 pm. The dimeric molecule shows nearly C2-symmetry, so that one lithium atom forms agostic bonds to both the trimethylsilyl groups, the other one to the tris(trimethylsilyl)silyl substituents. However, the 7Li{1H}-NMR spectrum displays a high field shifted singlet at —1.71 ppm. The lithiation of trimethylsilyl-[tris(trimethylsilyl)silyl]amine leads to a high field shift of the 29Si{1H} resonance of about 12 ppm for the Me3SiN group, whereas the parameters of the tris(trimethylsilyl)silyl ligand remain nearly unaffected. 相似文献
3.
选择"硅基芳胺的合成与表征"作为综合化学实验"无水无氧合成技术"的教学内容,实验涉及特殊用途玻璃仪器的干燥与组装、空气敏感物质的操作、惰性气体保护下的化学反应、溶剂浓缩、萃取、少量液体的减压蒸馏以及结构测定等操作。深入分析了无水无氧反应装置的准备、溶剂和物料的转移、正丁基锂的取用、双排管和施伦克玻璃仪器的使用等操作细节问题,并对产物的核磁共振氢谱进行了解析。通过该实验,学生能够实践较高层次的化学实验操作,对拓宽学生专业知识面、提高学生综合实验操作技能有良好的教学效果。 相似文献
4.
Nataliya F. Lazareva Tamara I. Vakul'skaya Igor M. Lazarev 《Journal of Physical Organic Chemistry》2009,22(2):144-154
This paper reports about high reactivity of α‐silylamines in the reaction with CCl4. Unlike Et3N, α‐silylamines rapidly react with CCl4 upon irradiation with daylight to form α‐silylamine hydrochloride salts in 92–98% yields. The influence of structure of α‐silylamines and solvent on the degree of conversion was displayed. The interaction of α‐silylamines with CCl4 was studied by NMR, ESR, and IR spectroscopy. C‐centered radicals of α‐silylamines were detected by ESR spectroscopy with spin traps (MNP, ND, and PBN) in reaction mixtures in CH3CN and C6H6 and it show the radical character of this reaction. Both CH3CN and C6H6 serve as solvents as well as reagents for this reaction. A mechanism of an interaction between α‐silylamines and CCl4 is discussed. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
5.
Kodai Ishihara Yuna Araki Prof. Mizuki Tada Prof. Tsutomu Takayama Prof. Yoichi Sakai Prof. W. M. C. Sameera Prof. Yasuhiro Ohki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9537-9546
Two transition-metal atoms bridged by hydrides may represent a useful structural motif for N2 activation by molecular complexes and the enzyme active site. In this study, dinuclear MoIV-FeII complexes with bridging hydrides, CpRMo(PMe3)(H)(μ-H)3FeCp* ( 2 a ; CpR=Cp*=C5Me5, 2 b ; CpR=C5Me4H), were synthesized via deprotonation of CpRMo(PMe3)H5 ( 1 a ; CpR=Cp*, 1 b ; CpR=C5Me4H) by Cp*FeN(SiMe3)2, and they were characterized by spectroscopy and crystallography. These Mo−Fe complexes reveal the shortest Mo−Fe distances ever reported (2.4005(3) Å for 2 a and 2.3952(3) Å for 2 b ), and the Mo−Fe interactions were analyzed by computational studies. Removal of the terminal Mo−H hydride in 2 a – 2 b by [Ph3C]+ in THF led to the formation of cationic THF adducts [CpRMo(PMe3)(THF)(μ-H)3FeCp*]+ ( 3 a ; CpR=Cp*, 3 b ; CpR=C5Me4H). Further reaction of 3 a with LiPPh2 gave rise to a phosphido-bridged complex Cp*Mo(PMe3)(μ-H)(μ-PPh2)FeCp* ( 4 ). A series of Mo−Fe complexes were subjected to catalytic silylation of N2 in the presence of Na and Me3SiCl, furnishing up to 129±20 equiv of N(SiMe3)3 per molecule of 2 b . Mechanism of the catalytic cycle was analyzed by DFT calculations. 相似文献
1