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Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

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Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
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Chemical substances interact in many different ways. Certain chemical reactions exhibit common patterns of reactivity. Due to the vast number of chemical reactions, it becomes necessary to classify them based on the observed patterns of interaction.
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Thermal Sigmatropic Reactions: Overview01:16

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Sigmatropic rearrangements are a class of pericyclic reactions in which a σ bond migrates from one part of a π system to another. These are intramolecular rearrangements where the total number of σ and π bonds remain unchanged.
Sigmatropic shifts are classified based on an order term [i, j ], where i and j indicate the number of atoms across which each end of the σ bond migrates. Below are examples of a [3,3] sigmatropic shift in 1,5-hexadiene, referred...
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Nuclear transmutation is the conversion of one nuclide into another. It can occur by the radioactive decay of a nucleus, or the reaction of a nucleus with another particle. The first manmade nucleus was produced in Ernest Rutherford’s laboratory in 1919 by a transmutation reaction, the bombardment of one type of nuclei with other nuclei or with neutrons. Rutherford bombarded nitrogen-14 atoms with high-speed α particles from a natural radioactive isotope of radium and observed...
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The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals. The new orbitals that...
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Predicting Precipitation
The equation that describes the equilibrium between solid calcium carbonate and its solvated ions is:
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Au25 (SR) 18とAg44 (SR) 30間のクラスター間反応

K R Krishnadas1, Atanu Ghosh1, Ananya Baksi1

  • 1DST Unit of Nanoscience (DST UNS) and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology Madras , Chennai, 600 036, India.

Journal of the American Chemical Society
|December 19, 2015
PubMed
まとめ

高貴な金属のクラスターは,原子とリガンドを交換し,自発的なクラスター間反応を経験します. この発見は,合金とドーピングの簡単な経路を提供し,単層保護クラスター化学を進めている.

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科学分野:

  • ナノ化学
  • 材料科学
  • 物理化学

背景:

  • 単層保護クラスター (MPC) は,ユニークな性質を持つ原子的に正確なナノ材料です.
  • 個々のMPC間の相互作用は,新しい材料とアプリケーションの開発に不可欠です.
  • MPCの反応メカニズムを理解することは,その制御された合成と機能化に不可欠です.

研究 の 目的:

  • 原子的に正確な貴金属のクラスターの間のクラスター間反応の最初の例を示します.
  • これらの反応のメカニズムと熱力学的実現可能性を調査する.
  • 合金とヘテロアトムドーピングのためのインタークラスター反応の可能性を調査する.

主な方法:

  • モデルシステムとして金 (Au25 ((SR) 18) と銀 (Ag44 ((SR) 30) のクラスタを使用した.
  • 反応産物を分析するために,電気スプレーのイオン化とマトリックスアシストレーザー脱吸収/イオン化質量スペクトロメトリーを使用した.
  • 熱力学的可行性を評価し,反応機構を提案するために,密度関数理論 (DFT) の計算を行った.

主要な成果:

  • 周囲の条件下でAuとAgのクラスター間の自発的なインタークラスター反応を観察した.
  • 反応中に金属原子とリガンドの交換を証明した.
  • 銀のヘテロアトムドーピングにより 20個の銀の原子を集約した黄金のクラスターに変換した.
  • メタルコア-チオラートインターフェースを反応開始と運動学にとって重要なものとして特定した.

結論:

  • クラスタ間反応は,合金高貴金属クラスタを作るための新しい経路を表しています.
  • この方法は,MPCを異なる金属原子でドーピングするための効率的な経路を提供します.
  • この発見は,単層保護クラスタのより広範な化学とその応用のための基盤を確立します.