+4酸化状態のTbの分子複合体

Chad T Palumbo¹, Ivica Zivkovic², Rosario Scopelliti¹

¹Insititut des Sciences et Ingénierie Chimiques , Ecole Polytechnique Fédérale de Lausanne (EPFL) , 1015 Lausanne , Switzerland.

Journal of the American Chemical Society

|June 14, 2019

まとめ

研究者らは,+4酸化状態の新しいテルビウム複合体を合成し,ランタニドの既知の化学構造を拡張した. この発見は,高値ランタニド化合物のユニークな性質を探求するための新しい道を提供します.

科学分野:

無機化学
ランタニド化学
酸化状態の化学

背景:

ランタニド (Ln) は分子化合物において主に+3と+2の酸化状態を示す.
ランタノイドの+4酸化状態は極めて稀で,以前は分子化合物でセリウム (Ce) しか分離されていなかった.

研究の目的:

テリビウム (Tb) の+4酸化状態のアクセシビリティを調査する.
分子Tb (IV) 複合体を合成し,特徴づけること.

主な方法:

テリビウム (III) 前駆体複合体, [KTb ((OSi ((O^tBu) 3) 4) ] (1-Tb) の酸化,トリス ((4-ブロモフェニル) アミニウム酸化剤を使用する.
固体構造の決定のためのX線結晶学Tb (III) とTb (IV) コンプレックス.
電子パラマグネティック共振 (EPR) スペクトロスコーピーと磁気計は,Tb(IV) 状態の明確な確認のために使用されます.

主要な成果:

分子テリビウム ((IV) 複合体の合成と分離が成功し, [Tb ((OSi ((O^tBu) 3)) ] (2-Tb).
X線結晶学による前駆体とTb (IV) 複合体の構造の解明.
Tb(IV) の酸化状態の確認は,スペクトル測定と磁気測定によって行われます.
電気化学分析では,2-Tbのリドックスポテンシャルが,そのCe (IV) アナログよりも約1V陽性であることが明らかになった.

結論:

+4酸化状態は分子テリビウム化合物で達成可能である.
合成されたTb (IV) 複合体は,Ce (IV) と比較してユニークな電気化学的性質を示している.
この研究は,高価ランタニド化学の既知の範囲を拡大する.

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