Synthesis and Structure of SnCl(CHSiMe): Toward Nanoclusters of 4-Coordinate α-Sn.

Orange crystals of a Sn cluster have been isolated in up to 22% yield from a reaction between MeSiCHSnCl, SnCl, and LiAlH. The structure determined by single crystal X-ray diffraction shows three unique Sn atoms in a 6:6:2 ratio, with all Sn atoms 4-coordinate, similar to the tetrahedral bonding in elemental gray Sn. The solid state Sn MAS NMR spectrum shows the three types of distinct Sn atoms in the expected 3:3:1 intensity ratio with respective chemical shifts of 87.9, -66.6, and -607.1 ppm relative to MeSn. The chemical shift of the two Sn atoms without ligands (bonded only to Sn), at -607.1 ppm, is the most upfield, and is the closest to the chemical shift, reported here, of bulk gray tin (-910 ppm). First-principles density functional theory calculations of the chemical shielding tensors corroborate this assignment. While the core coordination is distorted from the ideal tetrahedral arrangement in the diamond structure of gray tin, this Sn cluster, as the largest reported cluster with all 4-coordinate Sn, represents a major incremental step toward being able to prepare atomically precise nanoparticles of gray tin.