高价值基:证据表明U(VI) ((CH2SiMe3) 6的形成
Skye Fortier1, Justin R Walensky, Guang Wu
1Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.
Journal of the American Chemical Society
|June 24, 2011
概括
研究人员使用新氧化和化方法合成了高价值的基复合物,包括罕见的U (V) 和U (VI) 种. 这些发现促进了对化学和反应性的理解.
科学领域:
- 有机金属化学 有机金属化学
- 化学 的化学
- 协调化学 协调化学
背景情况:
- 基复合物对于理解的反应性至关重要.
- 高价值复合物的合成仍然具有挑战性.
- 探索新的合成途径以获得各种氧化状态是必不可少的.
研究的目的:
- 为了合成和表征新型高价值基复合物.
- 为了研究基复合物的反应性与不同的氧化剂.
- 探索这些新化合物的结构和电子特性.
主要方法:
- 一个同质的U(IV) 基复合物的氧化与和随后的化.
- 与三布坦醇反应,形成异构体U (IV) 和U (V) 复合体.
- 进行X射线晶体学,SQUID磁力测量和密度函数理论 (DFT) 分析以进行表征.
主要成果:
- 一个同质的U(V) 基复合物的成功合成, [Li(THF) ((4) ][U(CH ((2) SiMe ((3)) ((6) ] (1).
- 形成异构体U(IV) 和U(V) 复合体,包括具有银键的U(IV) 复合体.
- 一种罕见的U(VI) 基复合物的分离,U(CH(2) SiMe(3)) ((6) (6),稳定在-25°C以下.
结论:
- 新型合成策略使得人们可以获得高价值基复合物.
- 基的活性可以通过不同的配体和氧化剂来调整.
- 这项工作扩大了氧化状态和复杂结构的已知范围.
相关概念视频
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.
Acidity of 1-Alkynes
The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.
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.
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
Preparation of Alkynes: Dehydrohalogenation
Introduction
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Preparation of Alkynes: Alkylation Reaction
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.


