Facile Preparation of a Scandium Terminal Imido Complex Supported by a Phosphazene Ligand
作者:Rong, WF,Cheng, JH,Mou, ZH,Xie, HY,Cui, DM
关键字:h bond activation; actinide phosphinidene complexes; rare-earth; metal-complexes; structural-characterization; multiple bonds; reactivity; cleavage; existence; chemistry

The scandium bis(alkyl) complex bearing the phosphazene ligand L1Sc(CH2SiMe3)2 (1) (L1 = N(PPh2═NPh)2) reacted with an equimolar amount of 2,6-diisopropylaniline to afford the corresponding mixed alkyl/anilido complex L1Sc[NHC6H3(iPr)2](CH2SiMe3) (2). Under mild conditions (20 °C, 4 h or 0 °C, 12 h), complex 2 could be swiftly transformed to the terminal imido complex L1Sc═N[C6H3(iPr)2](DMAP)2 (4) in the presence of DMAP (DMAP = 4-N,N-dimethylaminopyridine). Correspondingly, treatment of the yttrium and lutetium bis(alkyl) complexes L2Ln(CH2SiMe3)2 (L2 = N[Ph2PNC6H3(iPr)2]2; Ln = Y (7), Lu (8)) with equimolar amounts of 2,6-diisopropylaniline gave the mixed alkyl/anilido complexes L2Ln[NHC6H3(iPr)2](CH2SiMe3) (Ln = Y (9), Lu (10)), which, however, underwent dealkylation of the Ln–CH2SiMe3species at temperatures of 60 °C for 9 and 100 °C for 10 to afford bis(anilido) complexes L2Ln[NHC6H3(iPr)2]2 (Ln = Y (11), Lu (12)) as redistribution products. All these complexes have been characterized by 1H, 13C{1H}, and 31P{1H} NMR spectroscopy and X-ray diffraction analyses, and clear structural insight into the behavior of an imido functionality on a lanthanide metal center was provided.