グループVIとVIIIの金属からのN-ヘテロサイクルカルベン-アミノボリレンリガンドの複合と放出
Conor Pranckevicius1,2, J Oscar C Jimenéz-Halla3, Marius Kirsch1,2
1Institute for Inorganic Chemistry , Julius-Maximilians-Universität Würzburg, Am Hubland , 97074 Würzburg , Germany.
Journal of the American Chemical Society
|July 27, 2018
まとめ
新しいアミノボリレンリガンドは,N-ヘテロサイクリックカルベン (NHC) によって安定し,堅固な金属複合体を形成する. これらのリガンドは高度に電子を放出し,核愛性であり,協調化学においてユニークな安定性と反応性を提供します.
科学分野:
- 有機金属化学
- メイングループ 化学
- リガンド設計
背景:
- N-ヘテロサイクリックカルベン (NHCs) は,協調化学における多用途リガンドである.
- アミノボリレン (aminoborylenes) は,独特の電子特性を有する,ボロンを含むリガンドのクラスである.
- メタルボリレン複合体の安定性と反応性を理解することは,新しい触媒システムの開発に不可欠です.
研究 の 目的:
- 異なるN-ヘテロサイクリックカルベン (NHC) 安定化群を持つアミノボリレンリガンドの調整化学と安定性を調査する.
- 新しい金属-アミノボリレン複合体を合成し,特徴づけること.
- NHCで安定したアミノボリレンと他のリガンドの電子特性と反応性を比較する.
主な方法:
- NHC-アミノボリレン複合体の合成,NHC-ジハロアミノボランアドクトの還元による.
- 還元剤として,ナトリウムヘキサカルボニルM0種 (M=Fe,Ru,Cr,W) の使用
- 赤外線光譜とX線結晶学を用いた特徴付け (暗示).
主要な成果:
- イミダゾル-2-イリデンで安定したアミノボリレンリガンドは,熱的に頑丈で惰性金属-ボリレン複合体を形成した.
- これらのリガンドは,古典的なNHCよりも電子を放出し,核愛性であることが判明した.
- サイクルアルキラミノカルベン (CAAC) に結合したダイハロアミノボランは,ボラン中心のラジカルまたはカルボニル安定したアミノボリレンを生成した.
- ボリレンからCOへの移行はルテニウム複合体で観察された.
結論:
- NHCで安定したアミノボリレンは,安定したユニークな金属複合体を作るのに有効なリガンドである.
- NHC安定化群の電子性質は,結果として得られるメタルボリレン複合体の反応性と安定性に大きく影響する.
- アミノボリレンは,触媒と材料科学における潜在的な応用を持つ新しいリガンドのクラスを表しています.
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