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ヘミケレーションは,電子不飽和複合体を安定させる方法である:T形のPdおよびPt金属サイクルのケース
Christophe Werlé1, Corinne Bailly, Lydia Karmazin-Brelot
1Institut de Chimie de Strasbourg, Université de Strasbourg, CNRS , 4 rue Blaise Pascal, F-67000 Strasbourg, France.
Journal of the American Chemical Society
|November 5, 2013
まとめ
新しい合成方法により,ユニークなクロームリガンドを使用して,安定したT形パラジウム (Pd) とプラチナ (Pt) コンプレックスを作成します. これらの持久性ヘテロメタリック化合物は,キュロンビック相互作用によって誘発される空の調整部位を特徴としています.
科学分野:
- 有機金属化学 有機金属化学
- 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:
- T形14電子複合体は,価値ある合成標的である.
- 不飽和金属中心の安定化は,有機金属化学における課題である.
研究 の 目的:
- 安定した中立のT型14電子パラジウム (Pd) とプラチナ (Pt) 複合体の合理的な合成を開発する.
- トリカルボニル (η) (6) -インデニル) クロミウムアニオンがヘミケラ化リガンドとしての有用性を調査する.
主な方法:
- PdとPtの金属サイクルのクロムアニオンの反応によるヘテロメタリック複合体の合成.
- 8つの新しい複合体の構造的特徴.
- NBO,EDA,ETS-NOCV,AIM,およびNCI分析を含む密度関数理論 (DFT) 方法を用いた理論的調査.
主要な成果:
- 空気に安定し,持続するシンファシアルヘテロメタリック複合体の形成.
- コンプレックスには η(1) -インデニル結合モードがあり,Pd/Ptセンターの調整部位が空いている.
- コンプレックス形成の熱力学的原動力は,Cr(CO) 3部分と空いた場所の間のクーロンビック引力として特定されました.
結論:
- 安定したT型14電子複合体PdとPtへの新たな合成経路が確立される.
- ヘミケリングインデニルクロミウムリガンドは,不飽和金属の中心を効果的に安定させます.
- DFT計算は,これらのユニークな二金属構造の結合と熱力学的安定性を明らかにします.
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