难以捉摸的OPN,是一种罕见的 σ2λ5-协调的例子
Xiaoqing Zeng1, Helmut Beckers, Helge Willner
1FB C-Mathematik und Naturwissenschaften-Fachgruppe Chemie, Bergische Universität Wuppertal, D-42097 Wuppertal, Germany.
Journal of the American Chemical Society
|November 26, 2011
概括
研究人员对酸三化物进行光解,形成了两个异构体:OPN和ONP. 这些异构体使用光谱学和同位素数据进行了表征,揭示了它们的光化学特性.
科学领域:
- 无机化学 无机化学 有机化学
- 摄影化学的使用.
- 矩阵隔离光谱法 矩阵隔离光谱法
背景情况:
- 酸三化物是一种前体分子,具有产生新化学物种的潜力.
- 了解富含的无机化合物的光化学路径对于合成化学至关重要.
研究的目的:
- 合成和表征酸衍生物的线性异构体.
- 为了研究这些同位素的光化学转换和特性.
主要方法:
- 矩阵隔离光谱 (中和远红外) 在冷温度 (16K).
- 使用ArF激光 (193nm) 和近紫外线/视光 (λ>320nm) 的光解.
- 使用同位素标记 ((14/15) N) 进行反应中间体的分离和表征.
主要成果:
- 两种线性异构体OPN和ONP已经成功形成和鉴定出来.
- 两个关键的中间体 (N(3)) ((2) P(O) N和N(3) P(O) N(4) 被分离和描述.
- 在ArF激光照射下观察到ONP到OPN的选择性光异构化.
结论:
- 该研究提供了OPN和ONP异构体的全面光谱特征.
- 阐明了涉及中间体的光化学途径,证明了选择性异构化.
- 结合实验和计算数据,讨论研究分子的特性.
相关概念视频
Hybridization of Atomic Orbitals II
sp3d and sp3d 2 Hybridization
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...
Exceptions to the Octet Rule
Many covalent molecules have central atoms that do not have eight electrons in their Lewis structures. These molecules fall into three categories:
Valence Bond Theory
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
Valence Bond Theory
Overview of Valence Bond Theory
Coordination Number and Geometry
For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.


