単原子二座標ビスムスを安定させる (I) とビスムスを安定させる (II) レドックス無害ビスムリン) リガンドを使用する
Jian Xu1, Sudip Pan2, Shenglai Yao1
1Metalorganic and Inorganic Materials, Department of Chemistry, Technische Universität Berlin, 10623 Berlin, Germany.
Journal of the American Chemical Society
|February 26, 2024
まとめ
研究者らは新しいビスムチンのリガンドを使用して,安定したビスムチンのリガンドを開発した. この戦略により,難題となるビスムート (I) とビスムート (II) の種を分離し,無機化学の新たな道を開くことができる.
科学分野:
- 無機化学
- 有機金属化学
- 材料科学
背景:
- 低価ビスムート (BiI,BiII) の種を分離することは,ビスムートの強い還元性により困難である.
- 反応性金属センターの安定化には,しばしば,電荷と酸化還元活性に対応できる特殊なリガンド設計が必要です.
研究 の 目的:
- 単一原子のBiIとBiII種を安定させるための戦略を開発する.
- リドックス非無害リガンドを用いた新しいビスムート複合体を合成し,特徴づけること.
主な方法:
- 新しいビス (イミノフォスファナミド-ゲルミレン) ザンテンのリガンドの合成
- コバルトセンを用いたBiIIII2の前駆体による2電子還元.
- DFT計算,X線光電子スペクトロスコーピー (XPS),電子パラマグネティック共振 (EPR) スペクトロスコーピーを用いた特徴付け.
- シングル電子移転 (SET) 反応を含む電気化学の研究.
主要な成果:
- 驚くほど安定したBiIカチオン複合体 (4) が合成され,新しいbis ((germylene)) リガンドが特徴付けられました.
- ゲルミレン部分への電荷移位はBiIセンターを安定させ,Pb0アナログと比較して安定性を高めました.
- リバーシブルな単電子酸化により,分離可能なBiIIラジカル複合体 (5) が得られ,不配列の電子は主にビスムースに含まれていた.
- BiIカチオンは高核愛性を示し,電友と反応してBiIII複合体を形成した.
結論:
- レドックス無害のビス・ゲルミレン・リガンドは,低価ビスムート種 (BiIとBiII) を効果的に安定させる.
- このアプローチは,分離可能で反応性のあるビスムート (I) とビスムート (II) コンプレックスへの便利な経路を提供します.
- 安定したビスマウト複合体は興味深い酸化還元能力と核愛性を示し,新しい合成変換の可能性を開きます.
さらに関連する動画
10:19Solution-Processed "Silver-Bismuth-Iodine" Ternary Thin Films for Lead-Free Photovoltaic Absorbers
Published on: September 27, 2018
9.7K
07:20Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
14.0K
関連する概念動画
02:51Metal-Ligand Bonds
20.8K
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...
20.8K
02:34Structural Isomerism
19.2K
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...
19.2K
01:09Complexation Equilibria: Factors Influencing Stability of Complexes
369
In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
369
02:42Valence Bond Theory
8.6K
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
8.6K
03:02Colors and Magnetism
11.7K
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...
11.7K
02:54Coordination Compounds and Nomenclature
21.4K
In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
21.4K