Privileged metal cluster complexes

• Published in: Chemical science (Cambridge) Vol. 16; no. 25; pp. 11619 - 11625
• Main Authors: Lin, Shiquan, Li, Dan, Zhang, Dandan, Geng, Lijun, Jia, Yuhan, Wang, Weizhe, Cheng, Longjiu, Khanna, Shiv N, Luo, Zhixun
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 25.06.2025
• Subjects: Coordination compounds; Ligands; Mass spectrometry; Metal clusters; Metal-metal bonding; Rhodium
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d5sc02924d

Clusters are a prominent subject of interest in modern chemistry research, bridging atoms and materials or catalysts. Metal coordination and metal-metal bonding are crucial in determining the chemical structures and properties of metal clusters; however, formulating a universal principle for assessing their electronic activity remains challenging. Utilizing self-developed mass spectrometry, this study examines the gas-phase reactions of rhodium and platinum clusters with common ligand molecules in forming metal complexes. We find that the Rh n ± ( n = 1-35) and Pt n ± ( n = 3-20) clusters readily react with CO and NO to form highly-selective products of cluster complexes. This illustrates the size-dependent saturable effect of sequential coordination, which is rooted in cluster stability alongside concurrent electron delocalization and local bonding. We introduce a new electronic rule, termed the electronic " A " rule, to understand the adaptive balance of electron delocalization and averaged local bonding in stabilizing metal clusters, whether they are coordinated with ligands or not. Gas-phase reactions of rhodium and platinum clusters with common ligand molecules in forming metal complexes, showing privileged cluster complexes with adaptive electron delocalization.