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ニッケル-鉄ヒドロゲナーゼモデルのプロトネーションは,ニッケルでのイソメリゼーション後に進行します
Mioy T Huynh1, David Schilter, Sharon Hammes-Schiffer
1Department of Chemistry, University of Illinois at Urbana-Champaign , Urbana, Illinois 61801, United States.
Journal of the American Chemical Society
|August 6, 2014
まとめ
ニッケル-鉄ディチオラートのプロトネーションは,鉄の部位で意外に起こりますが,鉄-ニッケル結合ではありません. この経路は,より基本的な,以前に検出されていなかった同位体を含み,他の金属複合体やクラスターに影響を与えます.
科学分野:
- オーガノメタリック化学
- 無機化学 無機化学とは
- 計算化学はコンピュータ化学である.
背景:
- ニッケル・鉄・ディチオラートは,触媒作用において重要である.
- 関連する金属複合体のプロトネーション機構は完全に理解されていません.
- 以前の研究では,金属対金属結合でプロトネーションが起こると示唆されていました.
研究 の 目的:
- 還元されたニッケル鉄ディチオラートのプロトネーション経路を調査するために.
- これらの複合体におけるプロトネーションの場所を特定するために.
- 反応メカニズムにおけるイソメアの役割を調査する.
主な方法:
- 鉄・ジチオラート・金属複合体 (M=Ni,Pd,Pt) の同類系を合成し,特徴づけること.
- 陽子化と1電子酸化を含む電気化学の研究.
- 密度関数理論 (DFT) の計算で,潜在エネルギー表面と同位体を探索する.
主要な成果:
- ニッケル-鉄複合体のプロトネーションは,鉄の部位で発生し,Fe(0) Ni(II) 同位体を形成し,Fe(I) -Ni(I) 結合は形成されません.
- Pd と Pt との複合体の同型系もプロトン化と酸化を経て,よく特徴づけられた水化物と混合バレンスの種を形成する.
- DFTの計算は,ニッケル-鉄複合体の正方形平面のNi部位を持つより基本的なFe(0) Ni(II) イソメアの存在を確認した.
結論:
- 還元されたNiFeディチオラートのプロトネーションは,これまで検出されていなかった,より基本的なFe(0) Ni(II) 同位体を通して行われます.
- この発見は,このような複合体におけるプロトネーション部位に関する以前の仮定に異議を唱えている.
- 発見された経路は,他の金属複合体やクラスターにおけるプロトナーションの理解に潜在的影響を及ぼします.
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