分散強化されたアルミニウム-銅およびガリウム-銅結合を特徴とする分子複合体
Kristian L Mears1, Cary R Stennett2, Elina K Taskinen3
1Materials Chemistry Centre, Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom.
Journal of the American Chemical Society
|November 10, 2020
まとめ
サポートされていない銅-アルミニウムと銅-ガリウム結合を持つ新しい銅複合体が合成されました. 密度関数理論の計算では,ロンドンの分散力が安定に大きく貢献していることが明らかになった.
科学分野:
- 協調化学
- 有機金属化学
- メイングループ 化学
背景:
- 銅 ((I) 複合体はβ-ダイケチミナートリガンドで,無機合成において多用途の前駆体である.
- β-ディケチミナートリガンドを持つ低価13族の金属複合体 (例えば,アルミニウム,ガリウム) は,ユニークな反応性を提供する.
- 支持されていない金属結合の形成は,無機化学における重要な課題である.
研究 の 目的:
- 金属と金属の結合を伴う 銅13組の複合体を合成する.
- これらの新しい化合物の構造的および電子的性質を特徴付ける.
- これらのユニークな金属対金属の相互作用を安定させる結合の貢献を調査する.
主な方法:
- 銅 ((I) β-ディケチミナート複合体と低価アルミニウムおよびガリウムβ-ディケチミナート複合体の反応.
- 銅-アルミニウムと銅-ガリウム複合体の分離と特徴付け
- 単一結晶X線 difraktionは分子構造と金属結合距離を決定する.
- 結合とエネルギー分析のための密度関数理論 (DFT) の計算.
主要な成果:
- {(BDIMes) CuAl(BDIDip) と {(BDIMes) CuGa(BDIDip) の複合体の合成に成功しました.
- これらの複合体は,銅-アルミニウムおよび銅-ガリウム結合がサポートされず,金属間距離が短い (Cu-Al = 2.3010 ((6) Å,Cu-Ga = 2.2916 ((5) Å).
- DFTの計算では,ロンドン分散力が計算された結合エンタルピーの約50%を占めていることが示されています.
結論:
- この研究は,β-ディケチミナートリガンドを使用して,サポートされていないCu-AlとCu-Ga結合を形成する可能性を実証している.
- 短い金属間距離は,重要な結合相互作用を示唆しています.
- ロンドン分散力は,これらの新種の有機金属化合物の安定化において重要な役割を果たします.
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