Carbonylative polymerization of oxetanes initiated by acetyl cobalt complexes.
Carbonylative polymerization of oxetanes initiated by acetyl cobalt complexes.
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DOI：
10.1002/asia.200700339
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发表时间：
2008-04
期刊：
影响因子：
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通讯作者：
Yessi Permana;K. Nakano;M. Yamashita;D. Watanabe;K. Nozaki
中科院分区：
文献类型：
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作者：
Yessi Permana;K. Nakano;M. Yamashita;D. Watanabe;K. Nozaki
四种乙酰基钴配合物[AcCo（CO）（3）P（p-tolyl）（3）]（1;对甲苯基=4-Me-C（6）H（4））、[AcCo（CO）（3）P（OPh）（3）]（2）、[AcCo（CO）（3）P（NMe（2））（3）]（3）和[AcCo（CO）（2）（dppp）]（4; dppp= 1，3-双（二苯基膦基）丙烷）的合成、表征和作为氧杂环丁烷的前所未有的羰基化聚合的催化剂的检验。含有酯（4-羟基链烷酸酯）和/或醚单元的共聚物，得到与配合物1和2，但不是与配合物3和4，无论是在存在或不存在额外的磷配体。酯/醚单元比在21：79-63：37范围内变化，并且通过在另外5当量的P（OPh）（3）存在下使用络合物1实现最高的酯/醚比63：37。虽然直接羰基化聚合是可能的，但也建议γ-内酯的预形成和开环作为替代途径。
Four acetyl cobalt complexes, [AcCo(CO)(3)P(p-tolyl)(3)] (1; p-tolyl=4-Me-C(6)H(4)), [AcCo(CO)(3)P(OPh)(3)] (2), [AcCo(CO)(3)P(NMe(2))(3)] (3), and [AcCo(CO)(2)(dppp)] (4; dppp=1,3-bis(diphenylphosphanyl)propane), were synthesized, characterized, and examined as catalysts for the unprecedented carbonylative polymerization of oxetanes. Copolymers containing ester (4-hydroxyalkanoate) and/or ether units were obtained with complexes 1 and 2, but not with complexes 3 and 4 either in the presence or absence of additional phosphorus ligands. The ester unit/ether unit ratio varied in the range 21:79-63:37, and the highest ester/ether ratio of 63:37 was achieved by using complex 1 in the presence of a further 5 equivalents of P(OPh)(3). Although direct carbonylative polymerization is possible, preformation and ring opening of the gamma-lactone is also suggested as an alternative pathway.