亜鉛ジサイラジドをLiClによって媒介された亜鉛水化物に変換する
Debabrata Mukherjee1, Arkady Ellern, Aaron D Sadow
1Department of Chemistry and U.S. Department of Energy Ames Laboratory, Iowa State University, Ames, Iowa 50011, USA.
Journal of the American Chemical Society
|May 18, 2010
まとめ
亜鉛 (((II)) と塩化リチウム (LiCl) を用いた新しいβ除去反応により,活性化されたシリコン-水素結合が生成されます. この反応では,Li (((+) とCl (((-) イオンが合力的に利用され,亜鉛水化物とサイクロディシラゼーンが形成されます.
科学分野:
- 有機金属化学 有機金属化学
- シリコン化学 シリコン化学
- 協調化化学について
背景:
- ディシラジド亜鉛化合物は,無機合成における既知の前駆体である.
- 有機金属化合物の反応を媒介するアルカリ金属ハリドの役割は完全に理解されていません.
- Si-H結合の活性化は,新しい合成方法論の開発に不可欠です.
研究 の 目的:
- 亜鉛 (II) とLiCl.Cl.を伴う異常なベータ除去反応を調査する.
- 反応メカニズムにおけるLi(+) とCl(-) イオンの相乗作用の解明.
- ディシラジド亜鉛化合物とLiCl.Clの反応により形成される製品の特徴を記述する.
主な方法:
- 座標的に飽和したジサイラジド亜鉛化合物と,THF/トルーエンの混合物におけるLiClの反応.
- 活性化されたSiH分子を含んだアドクトの形成.
- その結果生じる亜鉛水化物およびサイクロジサイラゼン製品の特徴.
主要な成果:
- LiClとdisilazido亜鉛化合物の間で形成されたアドクトは,SiH分子を活性化します.
- アドクトはTHF/トルーエンで亜鉛水化物とサイクロディシラゼーンに変換されます.
- Li(+) とCl(-) イオンは,どちらも単独でベータ除去を促進しないため,相乗効果で作用します.
- この反応は,正式なベータ除去経路を表しています.
結論:
- Li (((+) と Cl (((-) の相乗作用は,観察されたβ除去反応に不可欠である.
- この研究は,LiCl.によって媒介されるディシラジド亜鉛化合物の新しい反応経路を明らかにしています.
- この発見は,アルカリ金属ハリドが有機金属反応機構に及ぼす影響を理解するのに役立つ.
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