Synthesis and Characterization of Self-Supported Coordination Polymer Catalysts.

自支撑层状钯配位聚合物表现出优异的催化性能，远远超过固定化配位聚合物的催化性能。在本提案中，我们想利用这一结果并研究，这种更好的性能是否是这些配位聚合物催化剂的一般性质。因此，我们的目标是开发新的镝配位聚合物，评估其在碳转移反应中的催化性能，并通过固态核磁共振（如果必要的话结合DNP增强），SEM， TEM和AFM进行表征，以及催化剂的催化效率和对映选择性之间的关系，以及催化剂的结构和动力学性质。特别地，我们将使用13C CP MAS和19F MAS NMR来表征块状材料的结构，DNP增强19F-固态NMR来研究缺陷位点的数量和结构，以及变温度2H固态NMR（静态和MAS线形分析）来研究配位聚合物中桥接剂的动态行为。对于体配位聚合物的合成，将采用不同尺寸和功能的双位配体。通过配体大小调节层距，通过配体交换制备了不同体积的钯配位聚合物。本文将以苯乙烯和重氮乙酸乙酯之间的环丙化反应为模型反应，建立催化剂结构与催化效率之间的关系，对所得到的配位聚合物的催化效率和选择性进行评价。下一步，将合成含手性二羧基配体的重钠配位聚合物，并评价其在碳氢插入反应中的催化效率和对映选择性。最后，对层状体配位聚合物剥离制备的纳米薄片的催化性能进行了研究。

Self-supported layered dirhodium coordination polymers exhibit an excellent catalytic performance, which strongly exceeds the performance of its immobilized counterparts. In the present proposal, we want to exploit this result and study, whether such a better performance is a general property of these coordination polymer catalysts. Accordingly, our objectives are the development of novel dirhodium coordination polymers, the evaluation of their catalytic performance in carbene transfer reactions, and their characterization by solid-state NMR (if necessary combined with DNP enhancement), SEM, TEM and AFM, and a correlation between catalytic efficiency and enantioselectivity of the catalyst, and structural and dynamic properties of the catalyst. In particular we will employ 13C CP MAS and 19F MAS NMR to characterize the structure of the bulk materials, DNP enhanced 19F-solid state NMR spectroscopy to study the number and structure of defect sites and variable temperature 2H solid state NMR (static and MAS line-shape analysis) to investigate the dynamic behavior of bridging linkers in the coordination polymers. For the synthesis of bulk dirhodium coordination polymers, ditopic ligands with different sizes and functionality will be employed. By adjusting the layer distance via ligand size, various bulk dirhodium coordination polymers are prepared via ligand exchange. The resulting coordination polymers will be evaluated with respect to their catalytic efficacy and selectivity, employing the cyclopropanation between styrene and ethyl diazoacetate as model reaction to establish the relationship between the structure of the catalyst and its catalytic efficiency. In the next step, dirhodium coordination polymers containing chiral dicarboxylic ligands will be synthesized and their catalytic efficiency and enantioselectivity in C-H insertion reactions will be evaluated. Finally, the catalytic properties of nano-flakes prepared by exfoliation from the layered bulk-coordination polymers will be investigated.