1237503-09-1Relevant academic research and scientific papers
Intramolecular alkylation of α-diimine ligands giving amido-imino and diamido scandium and yttrium complexes as catalysts for intramolecular hydroamination/cyclization
Kaneko, Hiroshi,Tsurugi, Hayato,Panda, Tarun K.,Mashima, Kazushi
, p. 3463 - 3466 (2010)
Treatment of alkyl complexes M(CH2SiMe3) 3(THF)2 (1a: M = Sc; 1b: M = Y) with α-diimine ligands, N,N′-bis(2,6-dimethylphenyl)-1,4-diaza-1,3-butadiene (2a) and N,N′-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene (2b), afforded the corresponding amido-imino complexes M(CH2SiMe3) 2(2,6-R2Ph-DAB-CH2SiMe3)(THF) (3a: M = Sc, R = Me; 3b: M = Sc, R = iPr; 4a: M = Y, R = Me; 4b: M = Y, R = iPr) by selective monoalkylation of one of two C=N bonds of the ligands followed by intramolecular H migration, while in the reactions with a less bulky α-diimine ligand, N,N′-bis(4-methylphenyl)-1,4-diaza-1,3- butadiene (2c), complex 1a gave an diamido complex ScCH2SiMe 3(4-MePh-DAB-(CH2SiMe3)2)(THF) 2 (5c) as a product of the double alkylation. Upon heating a hexane solution of 3b, intramolecular activation of a C-H bond of an isopropyl group of the ligand proceeded to give a scandium monoalkyl complex ScCH 2SiMe3(CH2C2H4-6- iPrPh-2,6-iPr2Ph-DAB-CH2SiMe 3)(THF) (6b). Among them, amido-imino complexes of yttrium became catalysts for intramolecular hydroamination/cyclization of 2,2-dimethyl-4- pentenylamine at room temperature.
Living 3,4-polymerization of isoprene by cationic rare earth metal alkyl complexes bearing iminoamido ligands
Du, Gaixia,Wei, Yanling,Ai, Lin,Chen, Yuanyuan,Xu, Qi,Liu, Xiao,Zhang, Shaowen,Hou, Zhaomin,Li, Xiaofang
, p. 160 - 170 (2011/02/27)
Treatment of rare earth metal trialkyl complexes Ln(CH2SiMe 3)3(THF)2 (Ln = Sc, Lu, and Y) with 1 equiv of α-diimine ligands 2,6-R2C6H3N=CH-CH= NC6H3R2-2,6 (R = iPr, Me) affords straightforwardly monoanionic iminoamido rare earth metal dialkyl complexes [2,6-R2C6H3N-CH2-C(CH 2SiMe3)=NC6H3R2-2,6] Ln(CH2SiMe3)2(THF) (1: Ln = Sc, R = iPr; 2: Ln = Lu, R = iPr; 3: Ln = Y, R = iPr; 4: Ln = Sc, R = Me; 5: Ln = Lu, R = Me; 6: Ln = Y, R = Me) in 65-85% isolated yields. X-ray analyses show these complexes have decreasing steric hindrance in the coordination spheres of the metal centers in the order 1 > 2 > 3 > 4 > 5 > 6. A mechanism involving intramolecular alkyl and hydrogen migration is supported on the basis of DFT calculations to account for ligand alkylation. Activated by [Ph3C][B(C6F5) 4], all of these iminoamido rare earth metal dialkyl complexes are active for living polymerization of isoprene, with activity and selectivity being significantly dependent on the steric hindrance around the metal center to yield homopolyisoprene materials with different microstructures and compositions. The sterically crowded complexes 1-3 give a mixture of 3,4- and trans-1,4-polyisoprenes (3,4-selectivities: 48-82%, trans-1,4-selectivities: 50-17%), whereas the less sterically demanding complexes 4-6 show high 3,4-selectivities (3,4-selectivities: 90-100%). In the presence of 2 equiv of AliBu3, the complexes 1-6/activator systems exhibit higher activities and 3,4-selectivities in the living polymerization of isoprene. A similar structure-reactivity relationship in polymerization catalysis can be also observed in these ternary systems. A possible mechanism of the isoprene polymerization processes is proposed on the basis of the DFT calculations.
