稀土-ディニトロシリロン複合体からの窒素酸化物の結合と窒素酸化物の放出
Arun Kumar Bar1, María José Heras Ojea1, Jinkui Tang2
1Department of Chemistry, School of Life Sciences, University of Sussex, Brighton BN1 9QJ, U.K.
Journal of the American Chemical Society
|February 18, 2020
まとめ
ルイス酸性金属複合体は,ディニトロシリロン複合体 (DNIC) と反応し,新しいブリッジ構造を形成する. DNICの大量置換剤は,単一の鉄中心から異常なNOリガンド結合とN2Oの放出を誘発する.
科学分野:
- 有機金属化学
- 無機化学
- 協調化学
背景:
- ディニトロシルロン複合体 (DNIC) は,様々な化学的および生物学的プロセスにおいて重要である.
- DNICsとルイス酸の反応性は完全に理解されていません.
- 稀土元素は 独特の調整特性を備えています
研究 の 目的:
- ルイス酸 [Cp*2M]+ (M = Y,Gd) とディニトロシリロン複合体 [(NacNacAr) Fe ((NO)) 2−の反応を調査する.
- イソニトロシルブリッジドDNICの形成とその後の反応性を調査する.
- NOリガンドの結合とN2Oの放出に影響を与える要因を解明する.
主な方法:
- イソニトロシルブリッジドDNICの合成と特徴付け
- 構造を確認するための光譜分析 (例えば,NMR,IR).
- 異なる置換剤 (Ar) を含む,異なる条件下での反応性の調査.
主要な成果:
- イソニトロシル・ブリッジド DNIC の形成が達成された.
- Ar = 2,6-二イソプロピルフェニルでは,NOリガンド結合とN2Oの放出が観察された.
- 希土金属の酸化性と代替物の固体質は,重要な要因として特定された.
結論:
- この研究は,NOの結合とN2Oの除去を含むDNICの新しい反応モードを明らかにした.
- 稀土金属のルイス酸は,イソニトロシル結合の形成を促進し,NOリガンドを近接させます.
- DNICの巨大な置換物質からのステリック圧力は,NO結合の活性化バリアを克服し,単一の鉄センターからN2Oを放出します.
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