八面体的HSiCl3和HSiCl2Me附加物与化物
Gerrit W Fester1, Jörg Wagler, Erica Brendler
1Institut für Anorganische Chemie, TU Bergakademie Freiberg, Leipziger Strasse 29, 09596 Freiberg, Germany.
Journal of the American Chemical Society
|April 28, 2009
概括
合成了用化替代的化的稳定固体添加物. 这些化-化添加物表现出不同的稳定性和反应性,为控制水化等反应提供了洞察力.
科学领域:
- 有机化学 有机化学
- 协调化学 协调化学
- 材料科学 材料科学 材料科学
背景情况:
- 化基是已知的催化剂,用于涉及 (化) 西兰的反应.
- 了解西兰添加物的稳定性和反应性对于控制化学转化至关重要.
研究的目的:
- 用三西兰 (HSiCl3) 和二甲基 (HSiCl2Me) 替代化的稳定固体添加物进行合成和表征.
- 在不同的溶剂条件下研究这些添加物的稳定性和反应性.
- 为了阐明这些吸附复合体内的电子结构和粘合特性.
主要方法:
- 在近氧和无氧条件下合成添加物.
- 在极性溶剂中进行异变反应研究.
- 量化结构与活动关系 (QTAIM) 和费用分配分析.
- (29) Si 交叉极化魔力角旋转 (CP/MAS) 核磁共振 (NMR) 光谱学.
- 量子化学计算. 量子化学计算.
主要成果:
- 与HSiCl3和HSiCl2Me替代的化物 (Rpy) 的稳定固体添加物的高产量得到了实现.
- HSiCl3添加物在极性溶剂中发生了变异,而HSiCl2Me添加物显示出更大的稳定性,但由于降低了易斯酸度,更容易分离.
- 在QTAIM和电荷分布分析中,发现了高度有离子的-联体结合.
- (29) Si CP/MAS 核磁共振和计算研究揭示了沿Cl-Si-Cl,N-Si-N和H-Si-Cl/Me轴的屏蔽张数的特定方向.
结论:
- 化-化添加物的稳定性和反应性受化和溶剂极性的性质的影响.
- 联体结合的离子性质和确定的屏蔽张量组件为它们的电子结构提供了基本的见解.
- 这些发现为加强对胺催化反应的控制提供了基础,包括替代和含有西兰的水化工艺.
相关概念视频
Preparation and Reactions of Sulfides
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
Hybridization of Atomic Orbitals II
sp3d and sp3d 2 Hybridization
Electrophilic 1,2- and 1,4-Addition of HX to 1,3-Butadiene
The electrophilic addition of hydrogen halides such as HBr to alkenes and nonconjugated dienes gives a single product as per Markovnikov’s rule.
Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene
Electrophilic addition of halogens to alkenes proceeds via a cyclic halonium ion to form a 1,2-dihalide or a vicinal dihalide.
Acid Halides to Esters: Alcoholysis
Alcoholysis is a nucleophilic acyl substitution reaction in which an alcohol functions as a nucleophile. Acid halides react with alcohol to produce esters. The mechanism proceeds in three steps:
Electrophilic Addition to Alkynes: Halogenation
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.


