金属水素はハロゲン結合を形成する:結合エネルギーの測定
Dan A Smith1, Lee Brammer, Christopher A Hunter
1Department of Chemistry, University of York , Heslington, York, YO10 5DD, U.K.
Journal of the American Chemical Society
|January 2, 2014
まとめ
この研究では,酸化ヨドアルカンとビス (cyclopentadienyl) 金属水化物との間のハロゲン結合が実証されました. これらのハロゲン結合は,典型的な水素結合よりも強く,新しい化学相互作用の可能性を示しています.
科学分野:
- 有機金属化学 有機金属化学
- 超分子化学 超分子化学
- ハロゲン結合によるハロゲン結合
背景:
- ビス ((cyclopentadienyl) 金属水素は,多用途の有機金属化合物である.
- ハロゲン結合は,成長するアプリケーションで重要な非共性相互作用です.
- ハロゲン結合の強さを理解することは,新しい材料や触媒の設計に不可欠です.
研究 の 目的:
- フッ素化されたヨドアルカンと様々なビスチロペンタジニル金属ヒドリドの間のハロゲン結合の形成と強さを調査する.
- これらのハロゲン結合相互作用の熱力学パラメータを定量化するために.
- 同様のシステムにおけるハロゲン結合と水素結合の強さを比較する.
主な方法:
- プロトン核磁気共鳴 ((1) H NMR) спектроскопияは,ハロゲン結合形成を実証するために使用されました.
- 相互作用エンタルピーとエントロピーを決定するために,イソテルミックタイトレーション熱計 (ITC) が使用されました.
- より反応性の高い複合体については,低温関連定数を測定した.
主要な成果:
- ハロゲン結合は,イオドペンタフローロベンゼンと1-イオドペルフローロヘクサンの間にビス ((cyclopentadienyl) 金属水化物で成功裏に形成されました.
- C6F5IとC6F13Iとの複合体1の相互作用エンタルピーは,それぞれ -10.9 ± 0.4と -11.8 ± 0.3kJ/molであることが判明しました.
- これらのハロゲン結合はインドルとの水素結合よりも強く,ΔH°値は -7.3 ± 0.1 kJ/molであった.
結論:
- ビス ((cyclopentadienyl) メタルヒドリドは,有効なハロゲン結合受容体である.
- ハロゲン結合の強さは,金属センターとリガンドによって調節することができます.
- この研究は,有機金属系におけるハロゲン結合の性質と強さに関する貴重な洞察を提供します.
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