Synthesis and structure of a family of rhodium polystannide clusters [Rh@Sn10]3-, [Rh@Sn12]3-, [Rh2@Sn17]6- and the first triply-fused stannide, [Rh3@Sn24]5

Chao Liu; Xiao Jin; Lei-Jiao Li; Jun Xu; John E McGrady; Zhong-Ming Sun

doi:10.1039/c8sc03948h

Synthesis and structure of a family of rhodium polystannide clusters [Rh@Sn₁₀]^3-, [Rh@Sn₁₂]^3-, [Rh₂@Sn₁₇]^6- and the first triply-fused stannide, [Rh₃@Sn₂₄]⁵

Chem Sci. 2019 Mar 11;10(16):4394-4401. doi: 10.1039/c8sc03948h. eCollection 2019 Apr 28.

Authors

Chao Liu^{1

2}, Xiao Jin³, Lei-Jiao Li⁴, Jun Xu¹, John E McGrady³, Zhong-Ming Sun^{1

2}

Affiliations

¹ School of Materials Science and Engineering & National Institute for Advanced Materials , Tianjin Key Lab for Rare Earth Materials and Applications , Center for Rare Earth and Inorganic Functional Materials , State Key Laboratory of Elemento-Organic Chemistry , Nankai University , Tianjin 300350 , China . Email: sunlab@nankai.edu.cn ; http://zhongmingsun.weebly.com.
² State Key Laboratory of Rare Earth Resource Utilization , Changchun Institute of Applied Chemistry , Chinese Academy of Sciences , 5625 Renmin Street , Changchun , Jilin 130022 , China . Email: szm@ciac.ac.cn.
³ Department of Chemistry , University of Oxford , South Parks Road , Oxford OX1 3QR , UK . Email: john.mcgrady@chem.ox.ac.uk.
⁴ School of Chemistry & Environmental Engineering , Changchun University of Science & Technology , Changchun 130022 , China.

Abstract

Through relatively subtle changes in reaction conditions, we have been able to isolate four distinct Rh/Sn cluster compounds, [Rh@Sn₁₀]^3-, [Rh@Sn₁₂]^3-, [Rh₂@Sn₁₇]^6- and [Rh₃@Sn₂₄]^5-, from the reaction of K₄Sn₉ with [(COE)₂Rh(μ-Cl)]₂(COE = cyclooctene). The last of these has a hitherto unknown molecular topology, an edge-fused polyhedron containing three Rh@Sn₁₀ subunits, and represents the largest endohedral Group 14 Zintl cluster yet to have been isolated from solution. DFT has been used to place these new species in the context of known cluster chemistry. ESI-MS experiments on the reaction mixtures reveal the ubiquitous presence of {RhSn₈} fragments that may play a role in cluster growth.