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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Aggregated initiators: defining their role in the ROP of rac-lactide
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Aggregated initiators: defining their role in the ROP of rac-lactide

机译：汇总的发起人：定义他们在RAC丙交酯的roc中的作用

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摘要

Reported examples of aggregated initiators for the ring-opening polymerisation (ROP) of lactide often lack detailed investigations as to the nature of the active species, making it difficult to reconcile ligand design with performance. Here, we offer additional stability to the polynuclear titanium complexes, TiL(OiPr) (L = 9-14), through a bridging carboxylate anchored to the supporting amine bis(phenolate) ligands. An in-depth study of solution-state behaviour determined the process of assembly was driven by interactions between the carboxylate and a vacant site on a neighbouring titanium centre. Furthermore, we establish that mononuclear units form dynamic mixtures of polynuclear aggregates, with a clear relationship between nuclearity of the aggregates and the steric bulk on the ligand. Smaller aggregates displayed increased activity towards the ROP of rac-lactide. Furthermore, addition of a chiral centre, on the ligand framework, was investigated as a route to influence the selectivity of the polymerisation via easily-accessible initiators.
机译：报道的丙交酯的开环聚合（ROP）的聚集引发剂的实例通常缺乏对活性物种的性质的详细研究，使得具有性能的配体设计难以调和。在此，我们通过锚定向支撑胺双（酚酸盐）配体的桥接羧酸盐，为多核钛配合物，TIL（OIPR）（L = 9-14）提供额外的稳定性。对溶液状态行为的深入研究确定了通过羧酸盐与邻近的钛中心的相互作用的相互作用驱动组装过程。此外，我们建立单核单位形成多核聚集体的动态混合物，在聚集体的核性和配体上的核心之间具有明显的关系。较小的聚集体显示出对RAC丙交酯ROP的增加。此外，研究了配体框架上的手性中心作为影响聚合选择性通过易于可偏转的引发剂的途径。

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