Frustrated Lewis Pair-Like Reactivity of Rare-Earth Metal Complexes: 1,4-Addition Reactions and Polymerizations of Conjugated Polar Alkenes

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• 作者：Pengfei Xu ; Prof. Dr. Yingming Yao and Prof. Dr. Xin Xu
• 刊名：Chemistry - A European Journal
• 出版年：2017
• 出版时间：January 26, 2017
• 年：2017
• 卷：23
• 期：6
• 页码：1263-1267
• 全文大小：535K
• ISSN：1521-3765

文摘

Three rare-earth aryloxide ion pairs {[L1REOAr]⁺/[B(C₆F₅)₄]⁻; L1=CH₃C(2,6-iPr₂C₆H₃N)CHC(CH₃)(NCH₂CH₂PPh₂); RE=Sc, Y, Lu; Ar=2,6-tBu₂C₆H₃} were reported that feature rare-earth/phosphorus (RE/P) combinations exhibiting frustrated Lewis pair (FLP)-like 1,4-addition reactions towards conjugated carbonyl substrates (e.g., enone, ynone, and acrylic substrates). Furthermore, these RE/P complexes were found to be effective catalysts for the polymerization of conjugated polar alkene monomers. Mechanistic studies revealed that the rare-earth metal-catalyzed polymerizations were initiated by new FLP-type 1,4-additions rather than traditional and ubiquitous covalent RE−E (E=H, C, N, etc.) bond insertion or single-electron transfer.