Butyltin Keggin Ion with a Rare Four-Coordinate Ca Center.

Alkyltin clusters are exploited in nanolithography for the fabrication of microelectronics. The alkyltin Keggin family is unique among Keggin clusters across the periodic table; its members appear to favor the lower-symmetry β and γ isomers rather than the highly symmetrical α and ε isomers. Therefore, the alkyltin Keggin family may provide important fundamental information about the formation and isomerization of Keggin clusters. We have synthesized and structurally characterized a new butyltin Keggin cluster with a tetrahedral Ca center, fully formulated [(BuSn)(CaO)(OCH)(O)(OH)] (β-CaSn). The synthesis is a simple one-step process. Extensive solution characterization including electrospray ionization mass spectrometry, small-angle X-ray scattering, and multinuclear (H, C, and Sn) nuclear magnetic resonance shows β-CaSn is essentially phase-pure and stable. This differs from the previously reported Na-centered analogues that always form a mixture of β and γ isomers, with facile interconversion. Therefore, this study has clarified prior confusion over complex spectroscopic and crystallographic characterization of the Na-centered analogues. Density functional theory calculations showed the following stability order: γ-CaSn < γ-NaSn < β-CaSn < β-NaSn. The β analogue is always more stable than the γ analogue, consistent with experiment. Notable outcomes of this study include a rare tetrahedral Ca coordination, a Na-free alkyltin cluster (important for microelectronics manufacturing), and a better understanding of Keggin families built of different metal cations.