酸化原子がトリマンゲン複合体に移転し,Mn6 (((μ6-E) (E = O,N) のクラスターを形成し,中間酸化物と窒素酸化物の機能性を有する
Alison R Fout1, Qinliang Zhao, Dianne J Xiao
1Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge Massachusetts 02138, USA.
Journal of the American Chemical Society
|September 28, 2011
まとめ
研究者たちは,新しい三核マンガネス複合体を合成した. この複合体は,酸素と窒素の反応剤と反応して,ユニークなマイクロ(6) -オクソとマイクロ(6) -ナトリド六核マンガン複合体を形成し,無機化学を拡張します.
科学分野:
- 無機化学 無機化学とは
- 協調化化学について
- マテリアルサイエンス 材料科学
背景:
- マンガンの複合体は,様々な触媒プロセスにおいて極めて重要です.
- 特定の機能を持つ新しい多核マンガネス複合体の開発は,活発な研究分野です.
- 酸素や窒素などの小分子とのマンガネスクラスターの反応性を理解することは,新しい触媒を設計する上で鍵となるものです.
研究 の 目的:
- ヘクサデント酸リガンドを使用して,新しい三核マンガン複合体を合成し,特徴づけること.
- この複合体の酸素原子移転反応剤と無機アジドとの反応性を調査する.
- 結果となるオクソおよびニトリドの多核マンガン複合体の構造および電子特性を調査する.
主な方法:
- 三核マンガネス複合体の合成と特徴付け ((H) L) Mn ((3) ((thf) ((3)).
- 三核複合体のO原子移転反応剤との反応により,マイクロ(6) -オクソ複合体を形成する.
- 無機アジドとの反応により六核窒素化合物が形成され,その後に酸化が起こります.
- 電子パラマグネティック共振 (EPR) スペクトロスコピーとX線結晶学で,構造的および電子的分析を行う.
主要な成果:
- 新しい三核マングネス複合体 ((H) L) Mn ((3) ((thf) ((3)) が成功して合成されました.
- この複合体は,O-原子移転反応剤と共に,容易にマイクロ(6) -オクソ六核複合体を形成する.
- アジドとの反応により,六核性ニトリド複合体が生成され,さらに酸化することができる.
- EPRと構造分析は,オクソとニトリド複合体を区別し,異なるマンガンの酸化状態を明らかにしました.
結論:
- ヘクサデント酸リガンドプラットフォームは,安定した多核マンガン複合体の形成を可能にします.
- 合成された三核マンガネス複合体は,酸素と窒素種に対して多用途の反応性を示す.
- この研究は,マイクロ(6) -オクソとマイクロ(6) -ニトリドのマンガンのクラスターの構造的多様性と電子特性についての洞察を提供します.
関連する概念動画
01:21Radical Oxidation of Allylic and Benzylic Alcohols
Activated manganese(IV) oxide can selectively oxidize allylic and benzylic alcohols via a radical intermediate mechanism. Primary allylic alcohols are oxidized to aldehydes, while secondary allylic alcohols yield ketones. The redox reaction of potassium permanganate with an Mn(II) salt such as manganese sulfate (under either alkaline or acidic conditions), followed by thorough drying, yields the oxidizing agent: activated MnO2. While MnO2 is insoluble in the solvents used for the reaction, the...
02:58Properties of Transition Metals
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.
02:48Ionic Bonding and Electron Transfer
Ions are atoms or molecules bearing an electrical charge. A cation (a positive ion) forms when a neutral atom loses one or more electrons from its valence shell, and an anion (a negative ion) forms when a neutral atom gains one or more electrons in its valence shell. Compounds composed of ions are called ionic compounds (or salts), and their constituent ions are held together by ionic bonds: electrostatic forces of attraction between oppositely charged cations and anions.
02:57Coordination 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.
02:51Metal-Ligand Bonds
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...
03:02Colors and Magnetism
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 eye.
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 eye.