作为一个前所未有的大型光谱标记,C-O延伸用于铜 (II) 和酸离子之间的电子转移
Petr Milko1, Jana Roithová, Nikos Tsierkezos
1Faculty of Science, Department of Organic Chemistry, Charles University in Prague, Hlavova 8, 12843 Prague 2, Czech Republic.
Journal of the American Chemical Society
|May 16, 2008
概括
观察到[Cu(PhO) Ln]+复合物的C-O键振动频率发生显著的红色偏移,与连接物添加相关. 旋转密度的变化解释了观察到的债券顺序和频率的变化.
科学领域:
- 无机化学 无机化学
- 计算化学计算化学
- 频谱学是一种光谱学.
背景情况:
- C-O 键是各种化学系统中基本的功能组.
- 了解振动频率为分子结构和结合提供了洞察力.
- 铜复合物与氧联结物具有兴趣,因为它们的各种应用.
研究的目的:
- 为了研究联体添加对[Cu(PhO) Ln]+复合体中C-O键振动频率的影响.
- 阐明旋转密度分布与C-O键特性之间的关系.
- 报告一个前所未有的红色偏移在振动频率.
主要方法:
- 红外 (IR) 光谱法用于测量振动频率.
- 计算化学方法分析旋转密度和键序.
- [Cu(PhO) Ln]+复合物的合成和表征,具有不同的'n'.
主要成果:
- 在C-O振动频率中观察到一个前所未有的超过200厘米的红移.
- 红色转移的大小取决于额外连接体 (n) 的数量.
- 当n从1增加到2时,自旋密度从芳香环转移到氧和铜原子.
结论:
- 观察到的红色转移与C-O债券订单的变化直接相关.
- 旋转密度再分配在调节复合物的电子和振动性质方面发挥着至关重要的作用.
- 连接物环境显著影响铜氧复合物的结合和光谱特征.
相关概念视频
π Electron Effects on Chemical Shift: Aromatic and Antiaromatic Compounds
In aromatic compounds, such as benzene, the circulation of (4n + 2) π-electrons sets up a diamagnetic or diatropic ring current around the perimeter of the molecule. This current induces a magnetic field that opposes the external field inside the ring and reinforces it on the outside. The protons in benzene are deshielded and exhibit high chemical shifts in the range 6.5–8.5 ppm. The shielding effect at the center of the ring is evident in complex aromatic molecules, such as annulenes. In...
IR and UV–Vis Spectroscopy of Carboxylic Acids
In IR spectroscopy of carboxylic acids, the C=O bond shows a characteristic band between 1710 and 1760 cm⁻¹, and the O–H bond exhibits a broad band between 2500 and 3300 cm⁻¹.
However, the stretching absorptions for the C=O bond vary depending on the structure of carboxylic acids. The C=O bond of the free carboxylic acids shows a higher stretching frequency, 1760 cm−1, while H-bonded carboxylic acids (dimers) exhibit stretching absorptions at a lower frequency, 1710 cm−1. The C=O bond of the...
However, the stretching absorptions for the C=O bond vary depending on the structure of carboxylic acids. The C=O bond of the free carboxylic acids shows a higher stretching frequency, 1760 cm−1, while H-bonded carboxylic acids (dimers) exhibit stretching absorptions at a lower frequency, 1710 cm−1. The C=O bond of the...
π Electron Effects on Chemical Shift: Overview
An applied magnetic field causes loosely bound π-electrons in organic molecules to circulate, producing a local or induced diamagnetic field over a large spatial volume. As the molecules tumble in solution, the field generated by π-electrons in spherical substituents results in a zero net field. However, the net field generated by π-electrons in non-spherical substituents is not zero. The effect of this induced field depends on the orientation of the molecule with respect to B0, resulting in...
IR and UV–Vis Spectroscopy of Aldehydes and Ketones
Infrared spectroscopy, also known as vibrational spectroscopy, is mainly used to determine the types of bonds and functional groups in molecules. In aldehydes and ketones, the carbonyl (C=O) bond shows an absorption around 1710 cm-1. The C=O bond vibration of an aldehyde occurs at lower frequencies than that of a ketone. In addition to the C=O absorption in an aldehyde, the aldehydic C–H bond also gives two peaks in the 2700–2800 cm-1 range. This absorption, coupled with the C=O stretching, is...
IR Frequency Region: Alkene and Carbonyl Stretching
Double bonds in alkenes and carbonyl compounds exhibit stretching frequencies in the diagnostic region of the IR spectrum. In addition, alkenes exhibit vinylic C–H stretching and C–H out-of-plane bending absorptions that are useful for identifying substitution patterns.
Stretching frequencies are affected by several factors, such as resonance, inductive effects, ring strain, dipole moment, and hydrogen bonding. Consequently, the stretching frequency of the carbonyl double bond varies in...
Stretching frequencies are affected by several factors, such as resonance, inductive effects, ring strain, dipole moment, and hydrogen bonding. Consequently, the stretching frequency of the carbonyl double bond varies in...
Spectroscopy of Carboxylic Acid Derivatives
Infrared spectroscopy is primarily used to determine the types of bonds and functional groups. In carboxylic acid derivatives, a typical carbonyl bond absorption is observed around 1650–1850 cm−1. For esters, the absorption is recorded at around 1740 cm−1, while acid halides show the absorption at about 1800 cm−1. Another acid derivative, the acid anhydrides, exhibit two carbonyl absorption around 1760 cm−1 and 1820 cm−1, arising from the symmetrical and unsymmetrical carbonyl vibration.
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