的胺复合物:强大的PAr组转移载体到有机和无机基质
Benjamin F Wicker1, Jennifer Scott, José G Andino
1Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, Indiana 47405, USA.
Journal of the American Chemical Society
|March 4, 2010
概括
这项研究引入了第一个的胺复合体. 这些新型的酸复合物表现出反应性,作为各种有机和无机转换的前体.
科学领域:
- 有机金属化学 有机金属化学
- 主群 化学 化学
- 协调化学 协调化学
背景情况:
- 胺复合物是化学中的重要中间体.
- 复合体为连接体协调提供独特的电子和硬质性质.
研究的目的:
- 合成和描述了第一批的胺复合物.
- 研究这些新型复合物的反应性和连接体转移能力.
主要方法:
- 合成双核和单核酸酸复合物.
- 使用单晶X射线衍射和密度功能理论 (DFT) 研究进行表征.
- 对素联体转移到有机和无机基质的评估.
主要成果:
- 成功合成了双核[PNP]Sc[μ-P]Trip]和单核[PNP]Sc[μ-P]DMP]scandium phosphinidene复合物的成功合成.
- 通过离子封装,形成一种素盐衍生物,[(PNP) Sc(μ-P[DMP]) ((μ-Br) Li(DME).
- 从复合体向各种有机和无机基质证明了素联体的转移.
结论:
- 报道的酸复合物代表了一种新型的有机金属反应化合物.
- 这些复合物作为有效的素转移剂,扩大合成可能性.
- 通过全面的实验和计算分析,阐明了结构和电子特性.
相关概念视频
SN2 Reaction: Stereochemistry
In an SN2 reaction, the nucleophilic attack on the substrate and departure of the leaving group occurs simultaneously through a transition state. As the nucleophile approaches the substrate from the back-side, the configuration of the substrate carbon changes from tetrahedral to trigonal bipyramidal and then back to tetrahedral, leading to an inversion in the configuration of the product.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not observed.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not observed.
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
Chirality at Nitrogen, Phosphorus, and Sulfur
Chirality is most prevalent in carbon-based tetrahedral compounds, but this important facet of molecular symmetry extends to sp3-hybridized nitrogen, phosphorus and sulfur centers, including trivalent molecules with lone pairs. Here, the lone pair behaves as a functional group in addition to the other three substituents to form an analogous tetrahedral center that can be chiral.
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
SN2 Reaction: Transition State
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...
Predicting Molecular Geometry
VSEPR Theory for Determination of Electron Pair Geometries


