Abstract
Triorganotin(IV) chlorides containing one L CN chelating ligand were hydrolyzed with an excess of sodium hydroxide. The composition of the products is strongly dependent on the nature of the organic groups bound to the tin atom. Di( n-butyl)tin, dimethyltin as well as the diphenyl derivative exhibits an equilibrium between hydroxide and stannoxane forms (oxide), whereas alkyltin species react spontaneously and reversibly with carbon dioxide present in the air to form carbonate species. On the other hand, diphenyl derivatives display virtually no reaction with CO 2 towards carbonates, while the di- t-butyl-substituted tin derivative is stable under the same experimental condition and remains as a tin hydroxide. In the case of the dimethyltin derivative, a methyl group migration was observed with displacement of one L CN chelating ligand during the reaction on the air. The coordination geometry of the tin central atom(s) of all studied compounds can be described as trigonal bipyramidal with a dative bonded dimethylamino group occupying one coordination site. The catalytic activity of these compounds in transesterification reactions is generally lower compared to the systems reported in the literature, with the exception of the transesterification of ethyl acetate by cyclohexanol which displays a remarkable activity.
Published Version
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