title: Frustrated Lewis Pair-Like Reactivity of Rare-Earth Metal Complexes: 1,4-Addition Reactions and Polymerizations of Conjugated Polar Alkenes.
abstract: 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.
authors.affiliation: Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, P. R. China.
authors.forename: Pengfei
authors.initials: P
authors.lastname: Xu
authors.affiliation: Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, P. R. China.
authors.forename: Yingming
authors.initials: Y
authors.lastname: Yao
authors.affiliation: Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, P. R. China.
authors.forename: Xin
authors.initials: X
authors.lastname: Xu
keywords: cooperative effects; frustrated Lewis pairs; polymerization; rare earths