Reductive Dehydrocoupling of Diphenyltin Dihydride with LiAlH4: Selective Synthesis and Structures of the First Bicyclo[2.2.1]heptastannane-1,4-diide and Bicyclo[2.2.2]octastannane-1,4-diide

The reaction of diphenyltin dihydride with LiAlH4 gives access to a set of charged tin cages as their lithium salts. Variation in the ratio of reactants provides access to a perstannabicyclooctane dianion and a perstannanorbornane as the di- and monoanions. These compounds can be synthesised selectively by careful stoichiometric control and have been characterised by single crystal X-ray crystallography, NMR and UV-vis spectroscopy. Computational exploration of the electronic structures of these compounds was undertaken and, in agreement with structural and spectroscopic features, indicated significant σ-delocalisation in the tin skeletons.