単離可能なビスチレン) 安定したシリロンの合成と小ガス分子に対するその反応性
Yuwen Wang1, Miriam Karni2, Shenglai Yao1
1Metalorganics and Inorganic Materials, Department of Chemistry , Technische Universität Berlin , Straße des 17, Juni 135, Sekr. C2 , 10623 Berlin , Germany.
Journal of the American Chemical Society
|July 25, 2019
まとめ
研究者は,N-ヘテロサイクリックシリレンで安定した最初のゼロバレントのシリコン化合物を合成しました. この電子に富んだシリコン ((0) 化合物は驚くべき反応性を示し,アンモニアと小さな気体分子を活性化させ,シリコン化学の新たな道を開きます.
科学分野:
- オルガノシリコン化学
- メイングループ 化学
- 低バルントのシリコン化合物
背景:
- N-ヘテロサイクルのシリエレンは,反応性シリコン種の安定化に多用途のリガンドである.
- ゼロバレンスのメイングループ化合物は希少で,ユニークな反応性を示す.
- 低値シリコンの電子構造を理解することは,その振る舞いを予測するために不可欠です.
研究 の 目的:
- 最初の bis ((N-ヘテロサイクリックシリレン) -安定したゼロバレントのシリコン化合物を合成し,特徴づけること.
- 新種のシリコンの電子構造と結合を調査する.
- 小分子とルイス酸とのシリコン ((0) 化合物の反応性を調べる.
主な方法:
- クロロシリウムイリデン塩化物の前駆体による合成
- 顕微鏡 (NMR,IR) と結晶 (X線微分) による特徴付け
- 密度関数理論 (DFT) の計算と自然結合軌道 (NBO) の分析.
- N2O,アンモニア,BPh3,H2,エチレンによる反応性試験
主要な成果:
- 最初の bis ((N-ヘテロサイクリックシリレン) 安定したSi ((0) 化合物の合成が成功しました. [SiII(Xant) SiII]Si0
- 電子構造分析により,中央のSi0原子に2つの垂直単一ペアが発見された.
- N2Oによる制御された酸化によりSi4O2リングまたは1,4添加製品,NH3活性化,H2分裂,エチレン添加を含む,実証された反応性.
- BPh3による新しいルイスペアシステムの形成.
結論:
- 新しいシリコン ((0) 化合物は,安定した低値のシリコン種の新種を表しています.
- 電子が豊富な性質とユニークな電子構成により,多様な化学的変換が可能です.
- この研究は,シリレン化学と低価主群元素の反応性の範囲を拡大する.
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