3つの分子酸化状態における単核銅酸化物複合体の構造,光譜,および反応性
Tong Wu1, Samantha N MacMillan2, Khashayar Rajabimoghadam1
1Department of Chemistry, Southern Methodist University, Dallas, Texas 75275, United States.
Journal of the American Chemical Society
|June 13, 2020
まとめ
この研究は,高価な種を形成する可逆的な酸化を経験する新しい銅酸化物複合体を明らかにします. これらの複合体は強力な2H+/2e-酸化物質として作用し,銅媒介による電子移転反応に関する新しい洞察を提供します.
科学分野:
- 無機化学
- バイオ有機化学
- 材料科学
背景:
- 銅酸化物複合体は様々な触媒過程において極めて重要です.
- 銅複合体の電子構造と反応性を理解することは,新しい触媒の設計の鍵です.
- レドックス活性リガンドは,金属複合体に対して調節可能な電子特性を提供します.
研究 の 目的:
- 銅酸化物複合体の電子移転連鎖を合成し,特徴づけること.
- これらの複合体の構造的,スペクトル学的,および反応性の性質を調査する.
- 酸化のメカニズムと高価銅種の性質を明らかにする.
主な方法:
- 構造を決定するための単一結晶X線結晶学.
- 紫外線吸収,電子パラマグネティック共振 (EPR),およびX線吸収スペクトルスコピー (XAS) を特徴付ける.
- 酸化過程と反応性を研究するための電気化学的方法
主要な成果:
- 分子内H結合によって安定した単核 [CuOH]1+核が特定された.
- メタステーブルな高値CuOH種を生成する2つの可逆性酸化プロセスが観察されました.
- 顕微鏡データでは,リガンド局所化された酸化還元カップルが示された.
- 複合体は,既知の[CuOH]2+システムとは異なる2H+/2e-酸化行動を示した.
結論:
- この研究は,調整可能な酸化還元特性を持つ新種の銅酸化物複合体を提示する.
- この発見は,高価銅種を安定させるための酸化還元活性リガンドの役割を強調しています.
- これらの複合体は,化学的変異において効率的な2H+/2e-酸化物質としての可能性を示している.
![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
関連する概念動画
03:02Colors and Magnetism
13.6K
Color in Coordination Complexes
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...
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...
13.6K
01:26Photochemical Electrocyclic Reactions: Stereochemistry
2.1K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
2.1K
03:14Oxidation Numbers
41.9K
In redox reactions, the transfer of electrons occurs between reacting species. Electron transfer is described by a hypothetical number called the oxidation number (or oxidation state). It represents the effective charge of an atom or element, which is assigned using a set of rules.
41.9K
02:58Properties of Transition Metals
29.0K
Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
29.0K
01:12Cycloaddition Reactions: MO Requirements for Photochemical Activation
2.5K
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
2.5K
03:08Hydroboration-Oxidation of Alkenes
10.7K
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
10.7K