構造的に特徴付けられたμ-1,2-ペロキソ/スーペロキソ二銅 (II) ペア
Alexander Brinkmeier1, Roland A Schulz1, Moritz Buchhorn2
1Institut für Anorganische Chemie, Universität Göttingen, Tammannstraße 4, D-37077 Göttingen, Germany.
Journal of the American Chemical Society
|June 30, 2021
まとめ
この研究は,銅と酸素の化学における重要な中間物質であるスーパーオクソ二銅 (II) 複合体の最初の結晶構造を報告している. この構造的な洞察は,スーパーオクソとペロクソ・ディコッパー種の間の容易な相互変換を説明する.
科学分野:
- バイオ有機化学
- 協調化学
- 酸化触媒
背景:
- 銅の超酸化複合体は,酸素活性化メタロ酵素と酸化反応において不可欠である.
- 高度な反応性により 隔離や構造的特徴づけは困難です
- 以前の研究では,熱化学的データが確立されたが,二銅 (II) 超酸化物種の構造的な詳細は欠けていた.
研究 の 目的:
- 超酸化銅 (II) 種の最初の結晶構造を報告する.
- そのペロキシコンゲナーとそれらの相互変換を特徴づける.
- これらの重要な銅と酸素の中間物質の反応性に関する構造的な洞察を提供するためです.
主な方法:
- スーパーオクソとペロクソ二銅 (II) 複合体の結晶構造の決定
- レドックスポテンシャルと可逆性を決定する電気化学的研究.
- スペクトル解析 (IR,EPR) と磁気測定
- 密度関数理論 (DFT) の計算
主要な成果:
- 超酸化二銅 (II) 種 (3) とその過酸化同種 (2) の最初の結晶構造が決定された.
- 低電位 (-0.58 V 対 Fc/Fc+) で複合体2と3の相互変換が可逆である.
- 構造とスペクトロスコピーのデータは,O2誘導体の酸化還元活性を確認している.
- CuII-superoxo-CuII複合体はS=1/2スピンの基本状態を示している.
- DFT計算は二面角の変化のための浅い潜在エネルギー表面を明らかにします.
結論:
- この研究は,スーパーオクソ・ディコッパー (II) 複合体の最初の構造的特徴を示している.
- 構造と計算上の発見は,μ-1,2-スーパーオクソ/ペロクソ二銅 (II) カップルの容易で低再編成エネルギー相互変換を説明する.
- これらの結果は,銅-酸素化学および関連する酵素機構に関するさらなる調査のための基盤を提供します.
![[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
12.6K
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...
12.6K
02:52Stereoisomerism
12.8K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
12.8K
02:34Structural Isomerism
20.4K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
20.4K
02:21Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate
14.2K
Alkenes can be dihydroxylated using potassium permanganate. The method encompasses the reaction of an alkene with a cold, dilute solution of potassium permanganate under basic conditions to form a cis-diol along with a brown precipitate of manganese dioxide.
14.2K
02:51Metal-Ligand Bonds
22.5K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
22.5K
02:57Coordination Number and Geometry
17.2K
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.
17.2K