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Tris[(4-dimethylaminopyridyl) methyl]アミンを基にした最も活性な銅ATRP触媒の合成と特徴付け

Thomas G Ribelli¹, Marco Fantin¹, Jean-Claude Daran²

¹Department of Chemistry, Carnegie Mellon University , 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States.

Journal of the American Chemical Society

|January 11, 2018

まとめ

新しいリガンドであるtris[(4-dimethylaminopyridyl) methyl]amine (TPMA^NMe2) は,銅で触媒化された原子移転ラジカルポリメリゼーション (ATRP) を強化する. この高度に活性な触媒は,最小限の負荷と抑制された副作用で制御されたポリメリゼーションを可能にします.

科学分野:

ポリマー化学
カタリシス
有機金属化学

背景:

原子移転ラジカルポリメリゼーション (ATRP) は重要な制御されたポリメリゼーション技術です.
窒素ベースのリガンドを含む銅複合体は,ATRP触媒として広く使用されています.
より活発で効率的なATRP触媒の開発は,活発な研究分野です.

研究の目的:

新しいリガンド,トリス[(4-ジメチラミノピリジル) メチル]アミン (TPMA^NMe2) を合成し,特徴づけること.
ATRPにおけるTPMA^NMe2による銅複合体の触媒性能を評価する.
構造-活性関係と触媒の電気化学的性質を調査する.

主な方法:

TPMA^NMe2リガンドとその銅複合体の合成と特徴づけ
溶液の振る舞いを研究するための可変温度核磁気共振 (NMR) スペクトロスコーピー.
固体構造の決定のためのX線結晶学.
電気化学分析のための紫外線スペクトル検査とサイクル電圧測定 (CV)
CVを使用して活性化率定数 (k_a) と均衡定数 (K_ATRP) を決定する運動研究.

主要な成果:

[Cu^I(TPMA^NMe2) Br]複合体は溶液中の流動性を示し,迅速なリガンド交換を示している.
[Cu^II(TPMA^NMe2) Br][Br]複合体は,固体状態で歪んだ三角二ピラミッド幾何学を示している.
電気化学の研究では,非常にマイナスの酸化還元能力が示され,有意な触媒活性を示唆しています.
高活性化率定数 (k_a = 1.1 × 10⁶から7.2 × 10⁶ M^-1 s^-1) は,アクリラートおよびメタクリラートミミックについて決定された.
メチルアクリラートの良好なATRPは,超低触媒負荷 (10ppm) で達成された.

結論:

TPMA^NMe2は,非常に活性な銅ベースのATRP触媒を開発するための効果的なリガンドです.
触媒は優れた反応性と効率性を示し,非常に低い濃度で制御されたポリメリゼーションを可能にします.
Cu^I触媒による基幹終結 (CRT) のような副作用の抑制は,最適化された触媒性能により達成される.

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