The copolymerization of CO₂ and epoxides in the presence of chain-transfer agents (CTAs) has provided a well-controlled route to polycarbonate polyols. Upon employing dicarboxylic acid CTAs which contain discrete metal-binding sites, it is possible to synthesize polycarbonates with a single-metal complex present in the main chain, either during the copolymerization process or in a postpolymerization procedure. In these ways, the (bipy)Re(CO)₃Br complex has been incorporated into the polycarbonate backbone. Furthermore, in a one-pot, two-step synthesis, a second epoxide containing a vinyl substituent can be introduced to afford a triblock ABA polycarbonate, where the metal is contained in the B block. Subsequent to the thiol–ene click chemistry of HS^∧COOH and deprotonation, the resulting anionic polymer is shown to self-assemble in deionized water to provide rather uniform, spherical micelles. Since this procedure is modular, it is applicable to a wide variety of CTAs containing metal complexes or metal-binding sites, thereby providing a pathway to synthesize a wide range of micellar catalysts for pursuing organometallic transformations in water.

中文翻译：

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将单金属络合物放入基于CO ₂的聚碳酸酯链的骨架中，构建纳米结构以进行预期的胶束催化

在链转移剂（CTA）存在下，CO ₂和环氧化物的共聚为聚碳酸酯多元醇的制备提供了良好控制的途径。在使用包含离散的金属结合位点的二羧酸CTA时，可以在共聚过程中或在后聚合过程中合成具有主链中存在的单金属络合物的聚碳酸酯。通过这些方式，（bipy）Re（CO）₃ Br络合物已被引入聚碳酸酯骨架中。此外，在一锅两步合成中，可以引入包含乙烯基取代基的第二种环氧化物，得到三嵌段ABA聚碳酸酯，其中金属包含在B中。块。之后HS的硫醇-烯点击化学^∧在去离子水中COOH和去质子化，所得阴离子聚合物被示为自组装，以提供相当均匀的，球形胶束。由于该程序是模块化的，因此适用于包含金属配合物或金属结合位点的多种CTA，从而提供了合成多种胶束催化剂的途径，用于在水中进行有机金属转化。