Frustrated Lewis Pair-Like Reactivity of Rare-Earth Metal Complexes: 1,4-Addition Reactions and Polymerizations of Conjugated Polar Alkenes
Pengfei Xu, Yingming Yao*（姚英明）, Xin Xu*（徐信）
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, P. R. China
Chem.Eur.J.2017,23,1263–1267
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.
链接：http://onlinelibrary.wiley.com/doi/10.1002/chem.201605622/abstract