核性辅助和环开放聚合锡桥 [1] 铁烯烯的聚合
Thomas Baumgartner1, Frieder Jäkle, Ron Rulkens
1Department of Chemistry, University of Toronto, 80 St. George Street, Ontario, M5S 3H6, Canada.
Journal of the American Chemical Society
|August 22, 2002
概括
详细的研究揭示了桥 [1] ferrocenophanes 的环开放聚合 (ROP) 的新机制. 确定了核性和阴性通路,这表明杂质可以启动自发的ROP.
科学领域:
- 有机金属化学 有机金属化学
- 聚合物化学 聚合物化学
- 材料科学 材料科学 材料科学
背景情况:
- 锡桥 [1] 铁烯在环境温度下呈现自发环开聚合 (ROP).
- 了解这一ROP的机制对于控制聚合和开发新材料至关重要.
研究的目的:
- 阐明桥 [1] 铁烯的自发 ROP 的机械路径.
- 研究各种添加剂对聚合过程的影响.
- 提出新的ROP方法和机制.
主要方法:
- 详细的溶液相研究桥 [1] 铁烯 (R = t-Bu, Mes).
- 研究各种添加剂的作用:激素,核 (中性和阳离子),易斯酸,蛋白质物种和阴离子电.
- 在不同条件下的聚合率的动态分析.
主要成果:
- 提出了一种核性辅助的ROP机制,这种机制由像皮里丁这样的氨基核加速.
- 在添加电友物种 (H+,Bu3Sn+) 时观察到一个电离性ROP过程.
- 自发的ROP很可能是由微量易斯基或酸性杂质启动的.
结论:
- 已经确定了两种新型的ROP机制,用于应变 [1] 铁烯:核性辅助和阴性.
- 这些机制为铁烯的受控聚合提供了新的途径.
- 这些发现对含有14组元素的金属烯和金属循环的ROP具有更广泛的意义.
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