Thermal and Transition-Metal-Catalyzed Ring-Opening Polymerization (ROP) of [1]Silaferrocenophanes with Chlorine Substituents at Silicon: A Route to Tunable Poly(ferrocenylsilanes)
Thermal and Transition-Metal-Catalyzed Ring-Opening Polymerization (ROP) of [1]Silaferrocenophanes with Chlorine Substituents at Silicon: A Route to Tunable Poly(ferrocenylsilanes)
复制标题
硅上带有氯取代基的[1]硅二茂铁芬的热和过渡金属催化开环聚合（ROP）：制备可调节聚（二茂铁基硅烷）的途径
DOI：
10.1021/om950911v
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发表时间：
1996
期刊：
影响因子：
2.8
通讯作者：
D. Foucher
中科院分区：
文献类型：
--
作者：
D. Zechel;K. Hultzsch;R. Rulkens;David Balaishis;Yizeng Ni;J. Pudelski;A. Lough;I. Manners;D. Foucher
通过Fe(η-C5H4Li)2·TMEDA(η=四甲基乙二胺)分别与氯代硅烷MeSiCl3和SiCl4反应，在硅表面合成了含氯取代基的硅桥联二茂铁Fe(TMEDA-C5H4)2SiRR‘[3(R=Me，R’=Cl)，4(R=R‘=Cl)]。4的X射线衍射研究表明，该物种中的环戊二烯基环倾斜了19.2(4)°，这是其他结构表征的硅桥联[1]二茂铁的典型特征。3和4在2 5 0℃的热开环聚合反应合成了第一个含卤代硅基的高相对分子质量聚二茂铁基硅烷[Fe(η-C5H4)2SiRR‘]n[7(R=Me，R’=Cl)，8(R=R‘=Cl)].过渡金属催化的3和4在钯和铂催化剂上的聚合也在室温下得到聚合物7和8。聚合物7溶于极性有机溶剂，其结构经1H、29Si、13C核磁共振和元素分析确证。相比之下，聚二茂铁基硅烷8是...
The silicon-bridged [1]ferrocenophanes Fe(η-C5H4)2SiRR‘ [3 (R = Me, R‘ = Cl), 4 (R = R‘ = Cl)] with chlorine substituent(s) at silicon were prepared via the reaction of Fe(η-C5H4Li)2·TMEDA (TMEDA = tetramethylethylenediamine) with the chlorinated silanes MeSiCl3 and SiCl4, respectively. An X-ray diffraction study of 4 indicated that the cyclopentadienyl rings in this species are tilted by an angle of 19.2(4)°, typical of other structurally characterized silicon-bridged [1]ferrocenophanes. Thermal ring-opening polymerization (ROP) of 3 and 4 at 250 °C yielded the first high molecular weight poly(ferrocenylsilanes) with halogen substituents at silicon, [Fe(η-C5H4)2SiRR‘]n [7 (R = Me, R‘ = Cl), 8 (R = R‘ = Cl)]. Transition-metal-catalyzed polymerization of 3 and 4 with Pd and Pt catalysts also yielded polymers 7 and 8 in solution at room temperature. Polymer 7 was soluble in polar organic solvents and was characterized by 1H, 29Si, and 13C NMR and elemental analysis. In contrast, poly(ferrocenylsilane) 8 was...