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<p>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 CO<sub>2</sub> or 3-hexyne and H<sub>2</sub>, we discovered [Cu<sub>11</sub>Zn<sub>6</sub>](Cp*)<sub>8</sub>(CO<sub>2</sub>)<sub>2</sub>(HCO<sub>2</sub>) bearing a formate species related to CO<sub>2</sub> reduction and [Cu<sub>9</sub>Zn<sub>7</sub>](Cp*)<sub>6</sub>(Hex)<sub>3</sub>(H)<sub>3</sub> bearing C<sub>6</sub> species related to alkyne semi-hydrogenation.</p><p></p>

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

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年1月23日

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  • Raphael Bühler,
  • Max Schütz,
  • Karla F. Andriani,
  • Marcos G. Quiles,
  • João Paulo A. de Mendonça,
  • Vivianne K. Ocampo-Restrepo,
  • Johannes Stephan,
  • Sophia Ling,
  • Samia Kahlal,
  • Jean-Yves Saillard,
  • Christian Gemel,
  • Juarez L. F. Da Silva,
  • Roland A. Fischer

摘要

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.