Reaction products of dichlorodiorganostannanes with sodium in liquid ammonia: In-situ investigations with 119Sn NMR spectroscopy and usage as intermediates for the synthesis of tetraorganostannanes

Abstract

Dichlorodibutylstannane, dichlorodioctylstannane and dichlorodiphenylstannane were reacted with different amounts of sodium in liquid ammonia. At a molar ratio of R 2SnCl 2/Na of 1:2, polystannanes precipitated, in some cases accompanied by cyclic oligostannanes. The products resulting from mixtures with R 2SnCl 2/Na ratios of 1:3 to 1:10 were soluble and, hence, could be studied in-situ in liquid ammonia with 119Sn NMR spectroscopy. The compounds obtained, tin hydrides of the type R 2SnH − and in certain cases distannides of the composition R 4Sn 2 2−, formed essentially independent of the R 2SnCl 2/Na ratio; this, in contrast to views expressed in the literature. Our experiments showed that the chemical structure of the in-situ generated species did not permit to draw conclusions about the composition of the reaction products with bromoethane and vice versa – a practice commonly described. Furthermore, we observed migration of the butyl groups both in-situ during the reaction of dichlorodibutylstannane with sodium in liquid ammonia, as well as in the final reaction product. By contrast in the case of the phenyl substituent, migration was detected not during the chemical event in liquid ammonia, but only in the compounds formed. These observations imply a different mechanism for butyl and phenyl group migration.