德国慕尼黑工业大学Fischer, Roland A.团队报道了一个用于捕捉混合金属簇催化的动力学和反应性的活库概念。相关研究成果于2025年1月23日发表在《自然—化学》。

对连接金属团簇化学空间的探索具有挑战性，部分原因是对反应性团簇的靶向性不足。现在，通过有机金属前体化学获得团簇的动态混合物，定义为活库。这些库中充满了相互关联的集群，包括瞬态和高度反应性的集群，以及更容易获得但反应性较低的物种。监测它们在底物分子扰动下的演变，并在不分离簇的情况下获得化学信息。

该文中，研究人员准备了一个所有碳氢化合物连接的Cu/Zn团簇库，并开发了一个无偏差的计算框架，适用于分析整个组成空间，为每个团簇提供可靠的结构模型。这种方法能够有效地搜索与混合金属簇催化相关的结构-反应性关系：当用CO₂或3-己烯和H₂处理库时，发现 [Cu₁₁Zn₆](Cp*)₈(CO₂)₂(HCO₂)含有与CO₂还原相关的甲酸盐物种， [Cu₉Zn₇](Cp*)₆(Hex)₃(H)₃含有与炔烃半氢化相关的C6物种。

附：英文原文

Title: A living library concept to capture the dynamics and reactivity of mixed-metal clusters for catalysis

Author: Bhler, Raphael, Schtz, Max, Andriani, Karla F., Quiles, Marcos G., de Mendona, Joo Paulo A., Ocampo-Restrepo, Vivianne K., Stephan, Johannes, Ling, Sophia, Kahlal, Samia, Saillard, Jean-Yves, Gemel, Christian, Da Silva, Juarez L. F., Fischer, Roland A.

Issue&Volume: 2025-01-23

Abstract: The exploration of ligated metal clusters’ chemical space is challenging, partly owing to an insufficiently targeted access to reactive clusters. Now, dynamic mixtures of clusters, defined as living libraries, are obtained through organometallic precursor chemistry. The libraries are populated with interrelated clusters, including transient and highly reactive ones, as well as more accessible but less reactive species. Their evolutions upon perturbation with substrate molecules are monitored and chemical information is gained without separation of the clusters. Here we prepared a library of all-hydrocarbon ligated Cu/Zn clusters and developed a bias-free computational framework suited to analyse the full compositional space that yields a reliable structural model for each cluster. This methodology enables efficient searches for structure–reactivity relationships relevant for catalysis with mixed-metal clusters: when treating the library with CO2 or 3-hexyne and H2, we discovered [Cu11Zn6](Cp*)8(CO2)2(HCO2) bearing a formate species related to CO2 reduction and [Cu9Zn7](Cp*)6(Hex)3(H)3 bearing C6 species related to alkyne semi-hydrogenation.

DOI: 10.1038/s41557-024-01726-3

Source: https://www.nature.com/articles/s41557-024-01726-3