ニッケル協調球におけるEH2-置換シリレン (E=N,P,As) の多用途タウトメリゼーション
Terrance J Hadlington1, Tibor Szilvási2, Matthias Driess1
1Department of Chemistry, Metalorganics and Inorganic Materials , Technische Universität Berlin , Strasse des 17. Juni 135, Sekr. C2 , 10623 Berlin , Germany.
Journal of the American Chemical Society
|January 26, 2019
まとめ
この研究では,シリレンとその重ピニクトゲン (P,As) アナログを含む新しいニッケル複合体の合成が報告されています. これらの複合体は,移行金属化学におけるシリコン元素の多重結合の安定性およびタウトメリズムに関する新しい洞察を提供します.
科学分野:
- 有機金属化学
- シリコン化学
- 協調化学
背景:
- アミノシリレンとそのより重い類型は,無機合成における重要な構成要素である.
- シリコン元素の多重結合の反応性と安定性を理解することは,新しい触媒プロセスの開発に不可欠です.
- ニッケル複合体は,様々な有機変換で応用できる多用途の触媒である.
研究 の 目的:
- アミノシリレンとそれらのP-およびAs-アナログの新しいニッケル複合体を合成し,特徴づけること.
- これらのシリコン元素複合体のタウトメリゼーションと反応性を調査する.
- これらの新しい化合物の電子的性質と再配置プロセスを探求する.
主な方法:
- リチウムジヒドロプニクチドとクロロシリレンニッケル ((0) 複合体の塩分転移反応.
- シリレンニッケル複合体とのEH3 (E = N,P,As) のE-H結合活性化反応
- P-およびAs-アナログの変換によるニッケルサイクルの合成
- 電子的な性質と再配置プロセスを研究する量子化学計算.
主要な成果:
- サイドオン η2-RSi(H) EHとRH2Si-Eニッケル複合体の合成に成功した.
- 素因子 (N,P,As) に応じて異なるニッケル複合体を導いた容易なE-H結合活性化の観察.
- ニッケルサイクルの溶液中の安定性の変化を発見し,As-アナログは急速に再配置される.
- 高度分離電荷のメタライズド-η2-シアルセンのニッケル複合体を捕まえる.
結論:
- この研究は,サイド・オン・シラルディミン・トランジション・メタル・コンプレクスの相対的な安定性に関する最初の洞察を提供します.
- これらの複合体の電子的性質と再配置経路は明らかにされている.
- この研究は,調整複合体におけるシリコン元素多重結合化学の範囲を拡大する.
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