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01:13Olefin Metathesis Polymerization: Overview
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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
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01:16Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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01:26Thermal and Photochemical Electrocyclic Reactions: Overview
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Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
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Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
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01:22Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
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The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
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01:17Thermal Electrocyclic Reactions: Stereochemistry
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The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
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パイレン機能化されたル連鎖金属サイクル:加齢による連鎖システムの単方形への変換
Gajendra Gupta1, Junseong Lee2, Rizky Hadiputra3
1Department of Energy and Chemical Engineering/Innovation Center for Chemical Engineering, Incheon National University, Yeonsu-gu, Incheon 22012, Republic of Korea.
Journal of the American Chemical Society
|October 23, 2024
まとめ
ルテニウムとピレンから 新しく連鎖された長方形を合成しました これらの構造は 室温でナイトロメタンの単体四角形に自発的に変化し 分子の自己組織化に新たな洞察を与えます
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09:45Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
Published on: March 20, 2017
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10:51The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
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科学分野:
- 超分子化学
- 材料科学
- コンピュータ化学
背景:
- 機械的に結合した分子構造は 構造的な変化のために 化学的刺激を必要とします
- 自己組み立ての経路を理解することは 複雑な分子システムを設計するのに不可欠です
研究 の 目的:
- 新しいルテニウムとピレン基の 鎖状長方形を合成する
- 鎖状の長方形の構造が 単一長方形に変化する過程を研究する.
- 理論的な計算で連鎖構造の形成の熱力学的原動力を解明する.
主な方法:
- ルテニウムとピレンの構成要素を用いた (2+2) 2連鎖四角形の合成.
- 溶媒と濃度に依存する連鎖システムの構造分析.
- 密度関数理論 (DFT) とGFN2-xTB計算により,結合エネルギーと形成偏好を決定する.
主要な成果:
- ルテニウムとピレン基 (2+2) 2連鎖長方形の合成に成功した.
- 外部の化学操作なしに室温でニトロメタンで単角形に自発的に変容する観察.
- 理論的な計算により,連鎖構造は結合エネルギーが低いことが確認され,リング内構造やボロメ構造よりも形成が好ましいことが示された.
結論:
- 合成された鎖状の長方形は 絡み合った構造の 新しいクラスを表しています
- ニトロメタンの単角形への自発的な変容は,刺激のないユニークな分子行動を強調します.
- 計算上の洞察は,このシステムにおける連鎖アセンブリに対する熱力学的好みを検証する.