Synthesis, Structure and Chemical Bonding of Polyantimony Clusters Containing Coinage Metals [M2Sb14]4– (M = Cu, Ag)

• Published in: Chinese journal of chemistry Vol. 42; no. 6; pp. 617 - 622
• Main Authors: Chen, Wei‐Xing, Xu, Yu‐He, Wang, Cui‐Cui, Qiao, Lei, Guo, Zi‐Yan, Tian, Wen‐Juan, Sun, Zhong‐Ming
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY‐VCH Verlag GmbH & Co. KGaA 15.03.2024; Wiley Subscription Services, Inc
• Subjects: Antiaromaticity; Chemical bonds; Chemical synthesis; Clusters; Copper; Electronic structure; Ions; Metallophilic interaction; Metals; Polyantimony cluster; Quantum chemical calculations; Silver
• ISSN: 1001-604X; 1614-7065
• DOI: 10.1002/cjoc.202300606

Comprehensive Summary Binary polyantimony clusters, namely [Cu2Sb14]4– and [Ag2Sb14]4–, containing coinage metals, were successfully synthesized and characterized, in which two homoatomic Sb73– subunits are bridged by two coinage metals in η4:η1 and η1:η1 coordination modes, respectively. In [Cu2Sb14]4–, two bridging Cu ions and two Sb atoms form a planar rhombic unit, which was revealed to have antiaromatic properties by theoretical calculations. Further electron structure and bonding analysis confirmed the presence of delocalized bonds in the rhombic unit and the metallophilic interaction between two formal M+ ions. Two bimetallic Cu/Ag‐Sb clusters, [Cu2Sb14]4− and [Ag2Sb14]4−, comprising intact Sb7 units, were successfully synthesized and characterized. Quantum chemical calculations reveal that the rhombic Cu2Sb2 units within the [Cu2Sb14]4− cluster exhibit σ‐antiaromatic properties, and additional bonding analysis demonstrates that Cu∙∙∙Cu or Ag∙∙∙Ag interactions can be characterized as metallophilic interactions.