Group 4 Post-metallocene Complexes Incorporating Tridentate Silyl-Substituted Bis(naphthoxy)pyridine and Bis(naphthoxy)thiophene Ligands: Probing Systems for “Oscillating” Olefin Polymerization Catalysis
作者:Evgueni Kirillov、Thierry Roisnel、Abbas Razavi、Jean-François Carpentier
DOI:10.1021/om900550s
日期:2009.9.14
ONOSiPh3}Ti(OiPr)2 (8a) complexes were authenticated using NMR spectroscopy and X-ray crystallography methods for some of them. In the solid state, complexes 4a, 4b, and 6a feature rac-like binding of the ligand, while ligands in complexes 5b and 7a·(NHMe2) are meso-like coordinated. The solution structures of 4b and 5b were investigated by VT NMR spectroscopy, which revealed that both complexes exist as rac and meso
新的大体积甲硅烷基邻位取代的三齿2,6-双(萘酚)吡啶(ONO SiR3 } H 2,SiR 3 = SiPh 3,SiMe 2 t Bu)和2,5-双(萘酚)噻吩(OSO SiPh3 } H 2)前配体通过四步法合成。原配体ONO SiPh3 } H 2(3a)和OSO SiPh3 } H 2(3b)的固态结构通过X射线衍射分析确定。使用简单的一步式烷烃,胺或醇消除方案,将两种类型的配体引入第4组金属中心(M = Ti,Zr,Hf)。二苄基ONO SiPh3 } M(CH 2 Ph)2(M = Ti,4a ; Zr,5a ; Hf,6a)和ONO SiMe2 t Bu } M(CH 2 Ph)2(M = Ti,4b ; Zr,5b),二酰胺基ONO SiPh3 } Hf(NMe 2)2(7a和7a · (NHMe 2))和二(异丙氧基)ONO SiPh3 } Ti(O i