Hydrolysis of bis((trimethylsilyl)methyl)tin dihalides. Crystallographic and spectroscopic study of the hydrolysis pathway

The synthesis and characterization by multinuclear NMR spectroscopy of the diorganotin dihalides (Me₃SiCH₂)₂SnX₂ (<b>1</b>, X = Cl; <b>2</b>, X = Br), the diorganotin dichloride water adduct (Me₃SiCH₂)₂SnCl₂·H₂O (<b>1a</b>), the dimeric tetraorganodistannoxanes [(Me₃SiCH₂)₂(X)SnOSn(Y)(CH₂SiMe₃)₂]₂ (<b>3</b>, X = Y = Cl; <b>4</b>, X = Br, Y = OH; <b>5</b>, X = Br, Y = F; <b>6</b>, X = Y = OH; <b>8</b>, X = Cl, Y = OH), and the molecular diorganotin oxide <i>cyclo</i>-[(Me₃SiCH₂)₂SnO]₃ (<b>7</b>) are reported. The structures in the solid state of compounds <b>1a, 3, 6,</b> and <b>7</b> were determined by single-crystal X-ray analysis. In toluene solution, the hydroxy-substituted tetraorganodistannoxane <b>6</b> is in equilibrium with the diorganotin oxide <b>7</b> and water. The eight-membered diorganotin oxide <i>cyclo</i>-[(Me₃SiCH₂)₂SnO]₄ (<b>7a</b>) is proposed to be involved in this equilibrium. On the basis of the results of this and previous works, a general hydrolysis pathway is developed for diorganotin dichlorides containing reasonably bulky substituents.<br />