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Structural Isomerism02:34

Structural Isomerism

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 be...
Valence Bond Theory02:42

Valence Bond Theory

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...
Stability of Substituted Cyclohexanes02:30

Stability of Substituted Cyclohexanes

This lesson discusses the stability of substituted cyclohexanes with a focus on energies of various conformers and the effect of 1,3-diaxial interactions.
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
Stability of Conjugated Dienes01:28

Stability of Conjugated Dienes

Introduction
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic factors, steric factors also account...
Complexation Equilibria: Factors Influencing Stability of Complexes01:09

Complexation Equilibria: Factors Influencing Stability of Complexes

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...

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Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
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シリコン-シリコン三重結合を含む安定した化合物.

Akira Sekiguchi1, Rei Kinjo, Masaaki Ichinohe

  • 1Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan. sekiguch@staff.chem.tsukuba.ac.jp

Science (New York, N.Y.)
|September 18, 2004
PubMed
まとめ

研究者らは,安定したシリコン-シリコン三重結合化合物である1,1,4,4-テトラキス[bis(trimethylsilyl) メチル]-1,4-ジソプロピル-2-テトラシリンを合成した. このユニークな分子は,横折構造と驚くべき熱安定性を表しています.

科学分野:

  • オーガノシリコン化学 化学
  • 無機合成の無機合成について
  • マテリアルサイエンス 材料科学

背景:

  • シリコン原子間の複数の結合を特徴とする化合物の合成は困難です.
  • 以前の研究で,シリコン-シリコンの二重結合が探求されましたが,三重結合は依然としてほとんど難解です.
  • シリコン-シリコン多重結合の電子的および構造的性質を理解することは,シリコン化学の進歩に不可欠です.

研究 の 目的:

  • シリコン-シリコン三重結合を含む安定化合物を合成し,特徴づけること.
  • この新しいシリコン-シリコントリプルボンドの構造と結合特性を調査する.
  • シリコン-シリコン三重結合の性質を,炭素-炭素三重結合 (アルキン) の性質と比較する.

主な方法:

  • 2,2,3,3-テトラブロモ-1,1,4,4-テトラキス[bis(トリメチルシリル) メチル]-1,4-ジソプロピルテトラシランの反応は,テトラヒドロフランでカリウムグラフィート (KC8) と反応する.
  • 結果となる製品の分離と浄化.
  • 分子構造と結合長さを決定するX線結晶学.
  • 熱安定性の分析. 熱安定性の分析. 熱安定性の分析. 熱安定性の分析. 熱安定性の分析. 熱安定性の分析.

主要な成果:

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  • 1,1,4,4-テトラキス[bis(トリメチルシリル) メチル]-1,4-ジソプロピル-2-テトラシリンの合成が成功し,シリコン-シリコン三重結合を持つ安定化合物となった.
  • この化合物はエメラルド色の緑色の結晶を形成し,空気がない場合でも100°Cまで安定しています.
  • シリコン-シリコンのトリプルボンドの長さは2.0622 ((9) アングストロムと決定された.
  • シリコン-シリコン三重結合の周りの置換物質は,結合角度が137.44(4) 度であるトランスベント形状に配置されています.

結論:

  • 安定したシリコン-シリコン三重結合が初めて合成され,特徴づけられました.
  • シリコン-シリコンのトリプルボンドは,線形アルキンとは異なる,横曲線幾何学を含むユニークな構造特性を表しています.
  • シリコン-シリコンのトリプル結合における観察された結合の縮小は,アルキンとアルケンの比較でアルキンで見られる約半分であり,異なる結合特性を示唆しています.