Metalloid Tin Clusters, Sn _<i>n</i> <i>t</i> Bu _m , with α-Sn-Like Structural Motifs

High Resolution Image Download MS PowerPoint Slide Metalloid tin clusters represent an intriguing class of compounds that bridge molecular chemistry and the solid state, yet access to diverse examples remains limited. Herein, we present a mild, modular hydrostannolysis-type strategy that enables the synthesis of tin-based clusters stabilized by fairly small tert -butyl substituents, thereby overcoming the ligand-imposed structural limitations of established methodologies. The approach gave access to a series of clusters of different core sizes, including Sn 11 t Bu 12, featuring a [1.1.1]propellane-type backbone, as well as larger Sn 15 t Bu 14 and Sn 16 t Bu 16 derivatives adopting α-Sn-like core motifs with chair arrangement reminiscent of the diamond-type structure. Experimental characterization (X-ray crystallography and 119 Sn Mössbauer spectroscopy) and computational analyses (NBO and QTAIM) corroborate near-zero charges at the apical tin centers; the frontier orbitals show pronounced multicenter character across the tin framework, and several deeper-lying orbitals exhibit “superatom”-like character. Additionally, this synthetic protocol also afforded a unique, heterobimetallic Sn/Pb spiro compound, revealing the compatibility of the method with multiple group 14 elements.