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In this work, we report the synthesis and characterization of two novel Ru-containing Zintl clusters: [Sn19{Ru(COD)(en)}2]4− and [Sn20{Ru(COD)}2]6−. The synthesized compounds not only expand the family of Ru-Sn cluster systems but also shed light on the structure of heterometallic complexes in a previously unknown range of tin atoms. The single-crystal X-ray diffraction (XRD) analysis reveals the dimeric nature of the clusters. Two different assembly patterns of the formal [Sn(η3-Sn9)] monomer were observed: the dimerization through the vertex fusion process and the direct dimerization through the formation of 2c–2e Sn–Sn σ-bond. For both clusters, the density functional theory calculations reveal the locally σ-aromatic nature of the [Sn(η3-Sn9)] monomer resulting in two independent magnetic shielding cones. We believe that our findings will help the community to further explore the fascinating chemistry of polystannide clusters.
This work was supported by the National Natural Science Foundation of China (Nos. 92161102 and 21971118) and the Natural Science Foundation of Tianjin City (Nos. 20JCYBJC01560 and B2021202077) to Z. M. S. A. I. B. acknowledges financial support from the R. Gaurth Hansen Professorship fund. The support and resources from the Centre for High Performance Computing at the University of Utah are gratefully acknowledged. A. M. C. acknowledges financial support from FONDECYT 1180683. We also thank the valuable discussion from Professor Slavi C. Sevov (Department of Chemistry and Biochemistry, University of Notre Dame).