对双 (素) -稳定抗 (I) 离子的反应性研究
Nilanjana Mukherjee1, Vikas Kumar1, Cem B Yildiz2
1Department of Chemistry, Indian Institute of Science Education and Research, Pune, Dr. Homi Bhabha Road, Pashan, Pune 411008 Maharashtra, India.
Inorganic chemistry
|December 11, 2024
概括
这项研究引入了一种新型的Sb(I) 化合物,该化合物被素连接体稳定. 这种化合物表现出多种反应性,包括氧化和转化,并显示出在有机合成中作为易斯酸催化剂的潜力.
科学领域:
- 有机金属化学 有机金属化学
- 无机化学 无机化学 有机化学
- 催化剂是一种催化剂.
背景情况:
- 对低价值主要组元素化合物的探索对于理解基本化学键和反应性至关重要.
- 稳定低价值反 (Sb(I)) 化合物相对未被探索,为新的化学转化提供了机会.
- 氨酸连接体在稳定反应性主要组物种方面发挥着关键作用.
研究的目的:
- 为了合成和表征一种新型的5,6-Bis(diisopropylphosphino) acenaphthene (L) 稳定Sb(I) 阴离子化合物.
- 研究Sb(I) 中心对各种试剂的反应性,包括化剂,易斯酸和其他主要组化物.
- 在水化反应中评估合成的Sb(I) 和Sb(V) 化合物的催化潜力.
主要方法:
- 合成Sb(I) 化合物[LSb][OTf] (1) 和其后续反应.
- 使用单晶X射线衍射,多核NMR,质谱学和吸收光谱学对所有合成化合物的表征.
- 使用密度函数理论 (DFT) 来理解电子结构和反应机制的计算研究.
主要成果:
- 成功合成和表征了Sb(I) 化合物[LSb][OTf] (1).
- 化合物1表现出核友性行为,经过甲基三甲硫酸盐的氧化到[LSbMe][OTf]2 (2).
- 与易斯酸 (GaCl3,AlBr3) 的反应导致反离子交换,而与PI3的反应导致转化形成[LP][OTf] (5).
- 使用o-chloranil实现了Sb (I) 到Sb (V) 的氧化,产生了[L (O2C6Cl4) 2Sb][OTf] (6).
- 化合物1和6在p-甲基甲的水化中显示了路易斯酸催化活性的概念证明.
结论:
- 该研究成功合成和表征了一种新型Sb(I) 化合物,证明了其丰富的反应性.
- 这些发现强调了素稳定型Sb(I) 物种在经历氧化,转化和作为易斯酸催化剂的多功能性.
- 这项工作扩大了低价值主要组化学的范围,并为开发新的催化系统提供了潜力.
相关概念视频
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
1.8K
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...
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...
1.8K
α-Bromination of Carboxylic Acids: Hell–Volhard–Zelinski Reaction
2.9K
The method to achieve α-brominated carboxylic acids using a mixture of phosphorus tribromide and bromine is known as the Hell–Volhard–Zelinski reaction. The reaction is catalyzed by phosphorus tribromide, which can be used directly or produced in situ from red phosphorus and bromine. The mechanism comprises PBr3 catalyzed conversion of acid to acid bromide and hydrogen bromide. The acid bromide enolizes to its enol form in the presence of HBr. The nucleophilic enol attacks the...
2.9K
Preparation and Reactions of Sulfides
4.7K
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.
4.7K
Preparation and Reactions of Thiols
6.0K
Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.
6.0K
SN2 Reaction: Transition State
9.5K
An SN2 reaction of an alkyl halide is a single-step process in which bond formation between the nucleophile and the substrate and bond breaking between the substrate and the halide occurs simultaneously through a transition state without forming an intermediate.
When the nucleophile approaches the electrophilic carbon with its lone pairs, the halide acts as a leaving group and moves away with the electron-pair bonded to the carbon. Dotted partial bonds represent the bonds being formed or broken...
When the nucleophile approaches the electrophilic carbon with its lone pairs, the halide acts as a leaving group and moves away with the electron-pair bonded to the carbon. Dotted partial bonds represent the bonds being formed or broken...
9.5K
Radical Substitution: Allylic Bromination
5.0K
In organic synthesis, the formation of products can be altered by changing the reaction conditions. For example, a dibromo addition product is formed when propene is treated with bromine at room temperature. In contrast, propene undergoes allylic substitution in non-polar solvents at high temperatures to give 3-bromopropene. In order to avoid the addition reaction, the bromine concentration must be kept as low as possible throughout the reaction. This can be achieved using N-bromosuccinimide...
5.0K


