硫化ニッケルと一酸化炭素と一酸化窒素の反応性
Nathaniel J Hartmann1, Guang Wu1, Trevor W Hayton1
1Department of Chemistry and Biochemistry, University of California Santa Barbara , Santa Barbara, California 93106, United States.
Journal of the American Chemical Society
|September 9, 2016
まとめ
この研究では,硫化ニッケル複合体と一酸化炭素と一酸化窒素の反応が研究されています. 新しいニッケル複合体の形成と 生物系において重要なペルチオニートアニオンの形成を明らかにした.
科学分野:
- 無機化学
- 有機金属化学
- バイオ有機化学
背景:
- 移行金属硫化物は生物学的プロセスにおいて極めて重要です.
- 生物無機化学の鍵となるのが 小分子との反応性です
- ニッケル硫化物複合体は,そのような反応性を研究するためのユニークなプラットフォームを提供します.
研究 の 目的:
- 一酸化炭素 (CO) と一酸化窒素 (NO) とのマスクされた末端ニッケル硫化物の反応性を調査する.
- これらの反応から形成される産物を特徴づける.
- 窒素酸化物の反応からペルチオニートアニオンの形成を確認する.
主な方法:
- ニッケル硫化物複合体の合成と特徴付け [K(18-crown-6) ][L(tBu)) Ni ((II) ((S) ].
- 複合体は一酸化炭素 (CO) と一酸化窒素 (NO) と反応する.
- 生成したニッケル複合体とアニオンの分離と構造的決定.
主要な成果:
- ニッケル硫化物複合体は,COと反応して,カルボニル硫化物複合体,[K(18-クラウン-6) ][L(tBu)) Ni ((II) ((S,C:η ((2) -COS) ]を形成した.
- NOと反応すると,ニッケルニトロシル[L(tBu)) ,ペルチオニトリートアニオン[K(18-クラウン-6) ]SSNOが得られる.
- ペルチオニトリートアニオン (SSNO) の分離は,移行金属硫化物がNOと反応し,この生物学的に重要な種を形成する最初の証拠を提供します.
結論:
- マスクされたニッケル硫化物複合体は,COとNOに対して明確な反応性を示す.
- NO反応からペルチオニートアニオンの形成は,生物無機化学における重要な発見である.
- この研究は,移行金属硫化物複合体による小分子活性化の理解を拡大する.
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