カリックス[4]アレンカーセプレックスで4つのRh2 4+ファスナーが付いています
F Albert Cotton1, Peng Lei, Chun Lin
1Laboratory for Molecular Structure and Bonding, Department of Chemistry, P.O. Box 30012, Texas A&M University, College Station, Texas 77842-3012, USA. cotton@tamu.edu
Journal of the American Chemical Society
|February 5, 2004
まとめ
研究者は,カリックス[4]アレンを二重金属単位,トラッピング分子またはイオンと結びつけることで,安定した球状カルセプレクスを組み立てました. これらのケージは,驚くべき安定性を発揮し,結晶内のリガンド交換を可能にし,ダイナミックな宿主-ゲスト化学を実証しています.
科学分野:
- 超分子化学 超分子化学
- 協調化化学について
- マテリアルサイエンス 材料科学
背景:
- ゲストエンカプスレーションのための分子ケージの開発.
- カリックス[4]アリーンを複雑な建築の構成要素として利用する.
- 超分子組立における金属対金属結合ユニットを調査する.
研究 の 目的:
- 新しい球形状のカーセプレクスを合成し,特徴づけること.
- 分子およびイオンゲストの封じ込みを調査するために.
- カーセプレクスの安定性と動的性質を評価する.
主な方法:
- カリックス[4]アレンをディロジウム単位と結びつけることによって,カーセプレクスの組み立て.
- X線結晶学,NMR,IR,質量スペクトロメトリを用いた特徴付け.
- 単一結晶における軸性リガンド交換の調査.
主要な成果:
- トトラエチルアモニウムイオンを捕まえたテトラエチルアモニウムカルセプレックス (1b) の合成に成功.
- 高安定性および動的軸性リガンド交換 (アセトニトリル/水) の実証,結晶性の喪失なし.
- ディルホージウムとディモリブデンウム単位を持つ関連ダイメタル-カリキサレン化合物の特徴.
結論:
- 球形状のカルセプレックスは,カリックス[4]アレンと二金属単位から頑丈に構築できます.
- カーセプレクスは,かなりの安定性と調整可能なゲスト環境を示しています.
- 結晶内リガンド交換は,ダイナミックな超分子材料の可能性を強調しています.
関連する概念動画
Chair Conformation of Cyclohexane
The chair conformation is the most stable form of cyclohexane due to the absence of angle and torsional strain. The absence of angle strain is a result of cyclohexane’s bond angle being very close to the ideal tetrahedral bond angle of 109.5° in its chair conformer. Similarly, the torsional strain is also absent owing to the perfectly staggered arrangement of bonds.
The hydrogen atoms linked to carbons are arranged in two different axial and equatorial orientations to achieve this staggered...
The hydrogen atoms linked to carbons are arranged in two different axial and equatorial orientations to achieve this staggered...
Electrophilic Addition to Alkynes: Halogenation
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Criteria for Aromaticity and the Hückel 4n + 2 Rule
Like benzene, cyclobutadiene and cyclooctatetraene are cyclic compounds with alternate single and double bonds. However, their chemical behavior differs from benzene, as they are unstable and not aromatic. So, what are the structural characteristics of unsaturated compounds categorized as aromatic?
For the first time, Eric Hückel, a German chemical physicist, derived a set of structural features for a compound to be classified as aromatic. This is now known as Hückel’s rule or the 4n + 2 rule.
For the first time, Eric Hückel, a German chemical physicist, derived a set of structural features for a compound to be classified as aromatic. This is now known as Hückel’s rule or the 4n + 2 rule.
Five-Membered Heterocyclic Aromatic Compounds: Overview
Heterocyclic aromatic compounds are cyclic compounds that are aromatic and have one or more heteroatoms—atoms other than carbon, in the ring. Depending upon the number of atoms present in the ring, they can be either five or six-membered. Examples of five-membered heterocyclic aromatic compounds include pyrrole, furan, thiophene, and imidazole. Pyrrole consists of one nitrogen atom having one lone pair of electrons. Furan and thiophene have one oxygen and one sulfur heteroatom, respectively.
Frost Circles for Different Conjugated Systems
The inscribed polygon method is consistent with Hückel’s 4n + 2 rule and helps to learn whether the given cyclic compound is aromatic or not. The compound is stable and aromatic if every bonding molecular orbital (MO) is completely filled with a pair of electrons. However, if the non-bonding or antibonding orbitals are filled with electrons, the compound is unstable and not aromatic. Consider the Frost circle diagrams for cycloalkenes containing 4 to 8 carbons.
Aromatic Hydrocarbon Cations: Structural Overview
Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group with both...
Removing one hydrogen from the intervening CH2 group with both...


