ペロキシド化学の共鳴結合パターン: "フォスファディオキシラン"中間物質における周期的な3センターハイパー結合
Jeremiah J Wilke1, Frank Weinhold
1Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, USA.
Journal of the American Chemical Society
|September 7, 2006
まとめ
フォスファディオキシラン結合は高価ではない. 代わりに,ハイパーコーディネーションは,伝統的なルイス構造に挑戦する新しい周期的および線形の3センター,4電子 (3c/4e) のハイパーボンドから生じます.
科学分野:
- 無機化学 無機化学とは
- 理論化学 理論化学について
- コンピューティング・ケミストリー
背景:
- O(2) PR(3) "phosphadioxirane"中間物質の構造について議論されています.
- 伝統的なルイス構造は,5つの結合を持つ高価リンを示唆しています.
- 代替的な非高価結合パターンが提案されています.
研究 の 目的:
- フォスファディオキシラネスの結合性質を調査する.
- バルエンスシェル膨張とイオン共鳴の役割を決定する.
- これらの珍しい種のハイパーコーディネーションを明らかにするために.
主な方法:
- Ab initioとハイブリッド密度の関数計算.
- 自然共鳴理論 (NRT) を用いた理論分析.
- ナチュラル・ボンド・オービタル (NBO) を用いた理論分析.
主要な成果:
- ホスファドオキシランでは,ホスファドの真の高価性は無視できる.
- ハイパーコーディネーションは,線形ピメンテル=ランデル3c/4eハイパーボンドによって達成される.
- 前例のない周期的な3c/4eハイパーボンドパターンが特定されました.
結論:
- フォスファディオキシランのハイパーコーディネーションは,3c/4eハイパーボンドで説明されるが,d-オービタルハイパーヴァレンシーではない.
- この発見は,これらの種に対する従来の結合表現に異議を唱えている.
- この研究は,構造的表現と命名法への影響を調査しています.
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