Ladder Oxygenation of Group VIII Metal Clusters and the Formation of Metalloxocubes M13O8

• Published in: The journal of physical chemistry letters Vol. 13; no. 3; pp. 733 - 739
• Main Authors: Jia, Yuhan, Li, Jun, Huang, Miaofei, Geng, Lijun, Zhang, Hanyu, Cheng, Shi-Bo, Yi, Yuanping, Luo, Zhixun
• Format: Journal Article
• Language: English
• Published: American Chemical Society 27.01.2022
• Subjects: Physical Insights into Chemistry, Catalysis, and Interfaces
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.1c04098

The diversity of valence and bonding of transition metals makes their oxidation processes perplexing at reduced sizes. Here we report a comprehensive study on the oxidation reactions of rhodium clusters Rh n ± (n = 3–30) and find that Rh3,4O4 +, Rh5–7O6 +, and Rh8–13O8 + always dominate the mass distributions showing size-dependent ladder oxygenation which is closely associated with the O-binding modes. While the Rh8–13O8 + clusters display a μ3-O binding mode (hollow site adsorption), Rh3–4O4 + and Rh5–7O6 + favor the μ2-O binding mode (edge-site adsorption) or a mixture of the two modes. The μ3-O binding mode is inclined to yield a cubic Rh13O8, while the μ2-O binding mode gives rise to oxygen-bridge protection for the metal clusters. Such ladder oxidation was also observed for Pt n +, Fe n +, Co n +, and Ni n + clusters. We propose a three-dimensional diagram for the oxidation states and O-binding modes of metals, and highlight the metalloxocubes M13O8 + for cluster-genetic materials.