酸化窒素酸化窒素酸ナイトロシラートNi (I) とCu (I) C-オルガニニトロスアドクト
Stefan Wiese1, Pooja Kapoor, Kamille D Williams
1Department of Chemistry, Georgetown University, Box 571227, Washington, D.C. 20057-1227, USA.
Journal of the American Chemical Society
|December 17, 2009
まとめ
ニッケルと銅のβ-ディケチミナート複合体は,ArN=OのC-ニトロゾアドクトを形成し,多様な結合とN-O結合活性化を示す. これらの複合体はさらに酸化窒素と反応し,新しいN-アリル-N-ニトロソヒドロキシラミネート複合体を生成し,酸化性ニトロシル化を示す.
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
- 無機合成の無機合成とは
背景:
- ベータ-ディケチミネートリガンドを含む金属複合体は,協調化学において多用途である.
- 金属複合体の有機ニトロゾ化合物との反応は,N-O結合の活性化を理解する上で鍵となる.
- ArN=Oの単価ニッケルと銅複合体の反応性は完全に解明されていません.
研究 の 目的:
- ArN=Oを持つ単価ニッケルと銅のβ-ディケチミナート複合体の反応を調査する.
- その結果生成されるC-ニトロゾアドクトとその結合方式を特徴づける.
- これらの添加物の窒素酸化物 (NO) との後の反応性を調査する.
主な方法:
- ニッケルと銅のβ-ディケチミナート複合体の合成と特徴付け.
- 金属複合体の反応でArN=O (Ar = 3,5-Me(2) C(6) H(3), Ph) と反応してC-ニトロゾアドクトを形成する.
- 構造とN-O結合の活性化を決定するために,X線結晶学とIRスペクトロスコーピーを用いる.
- 孤立した添加物のガス状酸化窒素 (NO) との反応.
主要な成果:
- N-O結合の活性化が異なる3つの異なるC-ニトロゾアドクトの形成: {[Me(2) NN]Ni}(2) ((mu-eta(2):eta(2) -ONAr), {[Me(2) NN]Cu}(2) ((mu-eta(2):eta(1) -ONAr),および [Me(2) NN]Cueta(2) -ONAr).
- X線構造は,ArN=O分子の対称的および非対称的結合を明らかにし,N-O結合距離が著しく伸びている (最大1.440~4) Å).
- IRスペクトロスコーピーは915,1040,および1113 cm−1のアドクト形成 (ν(NO) によるN=O活性化の減少を確認しています.
- NOと反応すると,N-アリル-N-ニトロソヒドロキシラミナト複合体[Me(2) NN]M(カッパ(2) -O(2) N(2) Ar) (M = Ni, Cu) とニッケルニトロシル複合体が生成されます.
結論:
- 単価ニッケルと銅のβ-ディケチミナート複合体はArN=Oと効果的に反応し,多様なC-ニトロゾアドクトを生成する.
- これらのアダクトにおけるN-O結合活性化の程度は,金属と結合モードに基づいて調節可能である.
- これらのアダクトは,NOとの反応を通じた新しい有機金属複合体の前駆体として機能し,酸化性ニトロシル化の例を含む.
関連する概念動画
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