Hydrolysis of Bis((trimethylsilyl)methyl)tin Dihalides. Crystallographic and Spectroscopic Study of the Hydrolysis Pathway

Abstract

The synthesis and characterization by multinuclear NMR spectroscopy of the diorganotin dihalides (Me3SiCH2)2SnX2 (1, X = Cl; 2, X = Br), the diorganotin dichloride water adduct (Me3SiCH2)2SnCl2·H2O (1a), the dimeric tetraorganodistannoxanes [(Me3SiCH2)2(X)SnOSn(Y)(CH2SiMe3)2]2 (3, X = Y = Cl; 4, X = Br, Y = OH; 5, X = Br, Y = F; 6, X = Y = OH; 8, X = Cl, Y = OH), and the molecular diorganotin oxide cyclo-[(Me3SiCH2)2SnO]3 (7) are reported. The structures in the solid state of compounds 1a, 3, 6, and 7 were determined by single-crystal X-ray analysis. In toluene solution, the hydroxy-substituted tetraorganodistannoxane 6 is in equilibrium with the diorganotin oxide 7 and water. The eight-membered diorganotin oxide cyclo-[(Me3SiCH2)2SnO]4 (7a) 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.