フォスフィニデンの希土複合体における前例のない反応様式:共同実験理論研究
Haiwen Tian1, Jianquan Hong1, Kai Wang1
1Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University , Shanghai 200433, People's Republic of China.
Journal of the American Chemical Society
|December 23, 2017
まとめ
三核稀土金属複合体は様々な小さな分子と反応し,新しいリン化合物を形成します. 二酸化炭素とのユニークな反応は,異常なタンデム脱硫/結合/循環経路を明らかにします.
科学分野:
- 有機金属化学
- 希土金属複合体
- リン化学
背景:
- 機能化されたフォスフィニデン結合体を持つ三核稀土金属複合体は知られている.
- 小分子とのこれらの複合体の反応性は,現在進行中の研究分野です.
研究 の 目的:
- 三核の希土金属複合体と様々な小分子との反応を調査する.
- 反応メカニズムを解明し,その結果生成するリン含有産物を特定する.
- これらの複合体との二酸化炭素の異常な反応性を調査する.
主な方法:
- 三核稀土金属複合体の合成 [L3Ln3(μ2-Me) 2(μ3-Me) 3−η1:η2:η2-PC6H4-o) ] (Ln = Y, Lu)
- フェニラセチレン,CO2,ダイソプロピルカルボディミド,イソシアン化物,PhSSPh,およびCS2との反応
- 分析技術を用いた製品の特徴付け
- 反応経路を決定するための密度関数理論 (DFT) の計算.
主要な成果:
- さまざまな小分子との反応から一連のリン含有産物の形成.
- CS2との反応から2つの新しいP-メチル-フォスフィンドール-2,3-ディチオラートダイアニオン複合体を分離.
- CS2の異常なタンデム脱硫/結合/循環反応の観察
- DFTの計算は,フォスフィニデンのリガンドの還元力の役割を強調する提案された反応経路を支持した.
結論:
- 三核稀土金属のフォスフィニデン複合体は,小分子との多様な反応性を示す.
- 二酸化炭素は,脱硫,結合,循環を含むユニークなタンデム反応経路をたどります.
- フォスフィニデンのリガンドの還元力は,CS2反応におけるC-S結合の分裂に不可欠である.
関連する概念動画
Photoluminescence: Applications
1.1K
Photoluminescence offers a wide range of applications due to its inherent sensitivity and selectivity. This technique allows for both direct and indirect analyses of the analyte. Direct quantitative analysis is possible when the analyte exhibits a favorable quantum yield for fluorescence or phosphorescence. However, an indirect analysis may be feasible if the analyte is not fluorescent or phosphorescent, or if the quantum yield is unfavorable. Indirect methods include reacting the analyte with...
1.1K
Protein Kinases and Phosphatases
15.2K
Proteins undergo chemical modifications that trigger changes in the charge, structure, and conformation of the proteins. Phosphorylation, acetylation, glycosylation, nitrosylation, ubiquitination, lipidation, methylation, and proteolysis are various protein modifications that regulate protein activity. Such modifications are usually enzyme-driven.
Protein kinases
Many proteins in the cell are regulated by phosphorylation, the addition of a phosphate group. A family of enzymes called kinases...
Protein kinases
Many proteins in the cell are regulated by phosphorylation, the addition of a phosphate group. A family of enzymes called kinases...
15.2K
The Phosphorus Cycle
44.3K
Unlike carbon, water, and nitrogen, phosphorus is not present in the atmosphere as a gas. Instead, most phosphorus in the ecosystem exists as compounds, such as phosphate ions (PO43-), found in soil, water, sediment and rocks. Phosphorus is often a limiting nutrient (i.e., in short supply). Consequently, phosphorus is added to most agricultural fertilizers, which can cause environmental problems related to runoff in aquatic ecosystems.
44.3K
Predicting Molecular Geometry
46.2K
VSEPR Theory for Determination of Electron Pair Geometries
46.2K
Hybridization of Atomic Orbitals II
49.4K
sp3d and sp3d 2 Hybridization
49.4K
Chirality at Nitrogen, Phosphorus, and Sulfur
7.1K
Chirality is most prevalent in carbon-based tetrahedral compounds, but this important facet of molecular symmetry extends to sp3-hybridized nitrogen, phosphorus and sulfur centers, including trivalent molecules with lone pairs. Here, the lone pair behaves as a functional group in addition to the other three substituents to form an analogous tetrahedral center that can be chiral.
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
7.1K


