[L) AuCl]...[L') AuCl]ダイマーにおけるアオロフィリック相互作用:実験と理論による校正
Erik Andris1, Prokopis C Andrikopoulos2, Jiří Schulz1
1Department of Organic Chemistry, Faculty of Science, Charles University , Hlavova 2030, CZ-128 43 Prague 2, Czech Republic.
Journal of the American Chemical Society
|January 16, 2018
まとめ
金 (I) ダイマーにおける魅力的なオロフィリック相互作用は,複合体の安定性にとって極めて重要です. 水素結合に匹敵するこれらの相互作用は,充電された複合体と中性複合体の両方の実験的および理論的方法を使用して定量化されました.
科学分野:
- 無機化学
- コンピュータ化学
- 超分子化学
背景:
- 金属イオン複合体の安定化には,オーロフィルの相互作用を含むメタロフィルの相互作用が不可欠である.
- フォスフィンまたはN-ヘテロサイクルカルベンのリガンドを持つゴールド (I) 複合体は,これらの相互作用を研究するための一般的な標的である.
研究 の 目的:
- 閉殻黄金のダイマーにおけるオロフィリック相互作用の強さを実験的に理論的に評価する.
- これらの相互作用を計算するための量子化学的方法のベンチマーク.
- オーロフィリック,二極二極,およびインターリガンド分散力の貢献を比較する.
主な方法:
- 充電された金 (I) ダイマーに対する結合エネルギーのガス相実験的決定.
- 高レベルの相関量子化学計算 (CCSD) は,ベンチマークのためにSCS-MP2/CBSで校正されています.
- 中性金 (I) ダイマーに対する検証方法の適用
主要な成果:
- 充電されたダイマーには100−165 kJ mol−1,中性ダイマーには70−105 kJ mol−1の範囲にある.
- 純粋なアオロフィリック相互作用は,中性ダイマーで25〜30kJmol−1を寄与する.
- 二極対二極およびインターリガンド分散相互作用もまた,全体的な結合に大きく貢献する.
結論:
- 金 ((I) ダイマーのアオロフィリック相互作用は,強い水素結合の強さと同等またはそれ以上である.
- 実験と理論の組み合わせは,これらの重要な非共性相互作用の信頼性の高い定量化を提供します.
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