Ring‐opening polymerization of cyclic ethers initiated by benzazaphosphole‐W(CO)5/silver hexafluoroantimonate
Ring‐opening polymerization of cyclic ethers initiated by benzazaphosphole‐W(CO)5/silver hexafluoroantimonate
复制标题
DOI：
10.1002/pola.27047
复制
发表时间：
2014-03
期刊：
影响因子：
--
通讯作者：
M. Ghalib;S. Lysenko;P. Jones;J. Heinicke
中科院分区：
文献类型：
--
作者：
M. Ghalib;S. Lysenko;P. Jones;J. Heinicke
尝试通过苯并氮杂磷杂茂M（CO）5络合物1a-e（M = W，Mo，Cr）与AgSbF 6在THF中的反应来制备具有μ-桥接P配体的混合M（0）/Ag+络合物，导致该醚在室温下快速开环聚合，并且如1a/AgSbF 6所示，即使在低温下也是如此。氧杂环丁烷和环氧化物（氧化苯乙烯和氧化环己烯）在该引发剂的存在下甚至更剧烈地分解，并且需要用甲苯稀释以控制强放热反应。具有Ph 3 P、（EtO）3 P或2，4，6-三苯基膦配体的相关P（III）W（CO）5/AgSbF 6体系也引发THF聚合，但效率较低。在其他溶剂中分离引发剂络合物的努力失败，因为其对亲核试剂的高敏感性，并提供了2a，其通过晶体结构分析表征为甲醇在1a处的加成产物，尽管1a本身对MeOH稳定。© 2013 Wiley Periodicals，Inc. J.波利姆科学，A部分：聚合物Chem.2014，52，664-670
Attempts to prepare mixed M(0)/Ag+complexes with µ‐bridging P ligands by reaction of benzazaphosphole M(CO)5complexes1a–e(MW, Mo, Cr) with AgSbF6in THF lead to rapid ring‐opening polymerization of this ether at room temperature and, as shown for1a/AgSbF6, even at low temperature. Oxetane and epoxides (styrene oxide and cyclohexene oxide) polymerize even more vigorously in the presence of this initiator and require dilution with toluene to control the strongly exothermic reaction. Related P(III)W(CO)5/AgSbF6systems with Ph3P, (EtO)3P or 2,4,6‐triphenyl‐phosphinine ligands also initiate the THF polymerization, but less efficiently. Efforts to isolate the initiator complex in other solvents failed because of its high sensitivity to nucleophiles and provided2a,characterized by crystal structure analysis as the addition product of methanol at1a, although1aitself is stable towards MeOH. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem.2014,52, 664–670