Synthesis and Characterization of Self-Supported Coordination Polymer Catalysts.

自支撑配位聚合物催化剂的合成和表征。

• 批准号: 387282605
• 负责人: Professor Dr. Gerd Buntkowsky
• 金额: --
• 依托单位: Fachgebiet Physikalische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2017
• 资助国家: 德国
• 起止时间: 2016-12-31 至 2020-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/387282605?language=en
• 关键词: Synthesis; Characterization; Self; Supported; Coordination

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.

自支撑层状二铑配位聚合物具有优异的催化性能，远远超过了固载化的配位聚合物。在本提案中，我们希望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dirhodium配位聚合物，其在卡宾转移反应中的催化性能的评价，并通过固态NMR（如果需要结合DNP增强），SEM，TEM和AFM的表征，以及催化效率和催化剂的对映选择性之间的相关性，以及催化剂的结构和动力学性质。特别地，我们将使用13 C CP MAS和19 F MAS NMR来表征本体材料的结构，DNP增强的19 F-固态NMR光谱来研究缺陷位点的数量和结构，以及变温2 H固态NMR（静态和MAS线形分析）来研究配位聚合物中桥接连接体的动态行为。为了合成块状二铑配位聚合物，将采用具有不同尺寸和官能度的双配位配体。通过配体尺寸调节层间距，通过配体交换制备了各种块体二铑配位聚合物。以苯乙烯和重氮乙酸乙酯的环丙烷化反应为模型反应，考察了催化剂结构与催化效率的关系，并对所得配位聚合物的催化效率和选择性进行了评价。下一步，我们将合成含手性二羧酸配体的铑配位聚合物，并对其在C-H插入反应中的催化效率和对映选择性进行评价。最后，将研究由层状本体配位聚合物剥离制备的纳米薄片的催化性能。

项目成果

Design and characterization of novel dirhodium coordination polymers – the impact of ligand size on selectivity in asymmetric cyclopropanation

• DOI: 10.1039/d1cy00109d
• 发表时间: 2021
• 期刊: Catalysis Science & Technology
• 影响因子: 5
• 作者: Zhenzhong Li;Lorenz Rösler;T. Wissel;H. Breitzke;K. Hofmann;H. Limbach;T. Gutmann;G. Buntkowsky

SBA-15-Supported Imidazolium Ionic Liquid through Different Linkers as a Sustainable Catalyst for the Synthesis of Cyclic Carbonates: A Kinetic Study and Theoretical DFT Calculations

• DOI: 10.1021/acs.iecr.0c01050
• 发表时间: 2020-06
• 期刊: Industrial & Engineering Chemistry Research
• 影响因子: 4.2
• 作者: Zohre Dokhaee;M. Ghiaci;H. Farrokhpour;G. Buntkowsky;H. Breitzke

Coordination Compounds of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-Oxide (DOPO) Ligands: Extremely High Thermostability and Ligand Oxidation in the Solid State

• DOI: 10.1002/ejic.202000269
• 发表时间: 2020-06-23
• 期刊: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
• 影响因子: 2.3
• 作者: Goedderz, Daniela;Schaefer, Timmy;Doering, Manfred
• 通讯作者: Doering, Manfred

Insights into the role of zirconium in proline functionalized metal-organic frameworks attaining high enantio- and diastereoselectivity

• DOI: 10.1016/j.jcat.2019.07.003
• 发表时间: 2019-09
• 期刊: Journal of Catalysis
• 影响因子: 7.3
• 作者: K. Nguyen;Christel Kutzscher;S. Ehrling;I. Senkovska;V. Bon;M. de Oliveira;T. Gutmann;G. Buntkowsky;S. Kaskel

Novel Dirhodium Coordination Polymers: The Impact of Side Chains on Cyclopropanation

• DOI: 10.1039/c8cy01493k
• 发表时间: 2018-10
• 期刊: Catalysis Science & Technology
• 影响因子: 5
• 作者: Jiquan Liu;Yeping Xu;P. Groszewicz;M. Brodrecht;C. Fasel;K. Hofmann;X. Tan;T. Gutmann;G. Buntkowsky