Four-Membered Luteta heterocycles

作者：Thim Renita; Maichle Moessmer Caecilia; Anwander Reiner^*

来源：Organometallics, 2018, 37(15): 2563-2570.

DOI：10.1021/acs.organomet.8b00312

The four-membered metallacyclic lutetium complexes Tp(tBu,Me)Lu[CH2(SiMe2)NR] were synthesized via protonolysis of Tp(tBu,Me)LuMe(2) (Tp(tBu,Me) = hydrotris(3-methyl-5-tert-butylpyrazolyl)borato) with silylamines HN(SiMe3)R (R = SiMe3, C6H3(CF3)2-3,5 (Ar-CF3)). The sterically less demanding amine HN(SiHMe2)(2) led to the isolation of the heteroleptic complex (TLuMe)-Lu-ptBu,Me[N(SiHMe2)(2)]. The accessibility of the complex Tp(tBu,Me)Lu[CH2(SiMe2)NArCF3] to intramolecular ring opening was explored using HOCH(2)tBu, affording lutetium neopentoxide complexes Tp(tBu,Me)Lu[N(SiMe3)Ar-CF3](OCH(2)tBu) and (TLu)-Lu-ptBu,Me(OCH(2)tBu)(2). Treatment of (TLu)-Lu-ptBu,Me[CH2(SiMe2)NArCF3] with H3SiPh resulted in an unusual ring hydrogen/silyl group exchange and formation of Tp(tBu,Me)Lu[CH(SiH2Ph)(SiMe2)NArCF3], retaining the four-membered lutetaheterocycle. All complexes were fully characterized by NMR/IR spectroscopy, elemental analysis, and X-ray crystallography.

• 出版日期2018-8-13