Abstract
<jats:p> The reaction of Sn[N(SiMe <jats:sub>3</jats:sub> ) <jats:sub>2</jats:sub> ] <jats:sub>2</jats:sub> and 2,2′-methylenebis(4,6-dimethylphenol) <jats:bold>1</jats:bold> in THF generated a THF-coordinated dimer of diaryloxystannylene <jats:bold> [2·(thf)] <jats:sub>2</jats:sub> </jats:bold> , featuring a rhombic Sn <jats:sub>2</jats:sub> O <jats:sub>2</jats:sub> core. In contrast, conducting the reaction in toluene at 80 °C or in benzene at room temperature in the presence of small amount of H <jats:sub>2</jats:sub> O afforded a Sn <jats:sub>5</jats:sub> O <jats:sub>9</jats:sub> cluster ( <jats:bold>3</jats:bold> ), comprising a formal tin(II) oxide (Sn=O) and four diaryloxystannylene units. These products were characterized by NMR spectroscopy, single-crystal X-ray diffraction analysis, and elemental analysis. Structural analysis indicates that the tin(II) oxide fragment in <jats:bold>3</jats:bold> is best described as a charge-separated Sn+−O− unit rather than a Sn=O double bond, which is supported by DFT calculations. </jats:p>