铜的神话
Ida M DiMucci1, James T Lukens1, Sudipta Chatterjee1
1Department of Chemistry and Chemical Biology , Cornell University , Baker Laboratory, 162 Sciences Drive , Ithaca , New York 14853 , United States.
高价铜 (Cu) 复合体表现出高度共价的金属连接,使氧化状态的分配复杂化. 电子孔位于联体上,而不是铜,挑战传统的Cu (I) /Cu (III) 氧化还原描述.
科学领域:
- 无机化学
- 计算化学
- 光谱学
背景情况:
- 了解铜的氧化状态对于催化非常重要.
- 高价值的铜物种参与各种化学转化.
- 在铜复合体中准确地分配氧化状态可能是具有挑战性的.
研究的目的:
- 通过各种氧化状态来研究铜复合物的电子结构.
- 为了澄清高价值铜物种的金属连接的性质.
- 重新评估铜氧化过程的传统描述.
主要方法:
- 使用多端X射线吸收光谱 (XAS) 探测电子结构.
- 用密度函数理论 (DFT) 计算来建模和验证实验结果.
- 对X射线吸收数据进行了共价分析.
主要成果:
- 高价值铜 (Cu(III)) 复合体具有显著的金属配体共价性.
- K边缘和L2,3边缘的光谱表现出由共价键复杂的特征.
- 正式的Cu (III) 种在它们的LUMO中减少了Cu d的特征.
- 电子孔特征定位在支器上,而不仅仅是在铜上.
结论:
- 正式的Cu (III) 种的物理d8描述是不准确的.
- 铜具有有限的氧化能力,电子孔位于连接体上.
- 这项研究提供了另一种解释,以解释Cu (III) 物种在氧化还原过程中的反应性.
更多相关视频
09:12[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
10:31Detection and Recovery of Palladium, Gold and Cobalt Metals from the Urban Mine Using Novel Sensors/Adsorbents Designated with Nanoscale Wagon-wheel-shaped Pores
Published on: December 6, 2015
相关概念视频
Extraction: Advanced Methods
Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
Properties of Transition Metals
Exceptions to the Octet Rule
Valence Bond Theory
