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アニオニック・レニウム ((I) β-ディケチミナートによって生成される異金属Re-Zn-Zn-Re複合体

Trevor D Lohrey^1,2, Laurent Maron³, Robert G Bergman¹

¹Department of Chemistry , University of California, Berkeley , Berkeley , California 94720 , United States.

Journal of the American Chemical Society

|December 21, 2018

まとめ

この研究は,新しいアニオン性レニウム ((I) 化合物,Na[Re ((η5-Cp)) ((BDI)) を導入し,強力な還元剤およびメタロリガンドとしての有用性を実証した. この研究は,レニウム (II) とレニウム (III) 複合体,およびユニークな四金属亜鉛-レニウム核への変換を調査する.

科学分野:

有機金属化学
協調化学
非有機合成

背景:

レーニウム複合体は,触媒と材料科学で価値があります.
新しい酸化状態と有機金属化合物の結合を探求することは極めて重要です
強力な化学的還元剤と多用途の金属リガンドの開発は,依然として活発な研究分野である.

研究の目的:

新しいアニオンリニウムの化合物を合成し,特徴づけること.
還元剤とメタロリガンドとしてのレニウム (I) 複合体の反応性を調査する.
多核亜鉛-レニウム複合体の形成と電子構造を調査する.

主な方法:

アニオン型レニウム ((I) コンプレックスNa[Re ((η5-Cp)) ((BDI)) の合成.
異なるレニウムの酸化状態に到達するための化学的酸化およびプロトネーション反応.
ZnCl2と反応して四金属亜鉛-レニウム化合物を形成する.
金属と金属の結合を分析するための計算研究 (DFT).

主要な成果:

Na[Re ((η5-Cp)) ((BDI)) の合成が成功しました.
レーニウム (II) (2) とレーニウム (III) 水素 (3) の複合体の形成.
化合物4でテトラメタルのRe (I) -Zn (I) -Zn (I) -Re (I) 核を発見した.
デイティブのRe-ZnとコヴァレンスのZn-Zn相互作用を含む4における金属結合の特徴.
4の酸化によりレニウム (II) 複合体2と亜鉛 (II) 複合体5が得られる.

結論:

アニオンリニウム ((I) 複合体は,多様なリニウム酸化状態とユニークな多核構造にアクセスするための多機能な前駆体である.
テトラメタリック・コアにはレンと亜鉛の中心との興味深い電子相互作用があります
この研究は,オルガノレニウム化学と金属結合の研究の範囲を拡大する.

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