Oxidative-addition reactions of molecular diiodine and dibromine to divalent organotin compounds. Crystal structures of bis[8-(dimethylamino)-1-naphthyl]tin(IV) dibromide and {2,6-[bis(dimethylamino)methyl]phenyl}- (4-tolyl)tin(IV) diodide

Abstract

The reactions of bis[8-(dimethylamino)-1-naphthyl]tin(II) with dibromine or diiodine afford bis[8-(dimethylamino)-1-naphthyl]tin(IV) dibromide ( 1) and bis[8-(dimethylamino)-1-naphthyl]tin(IV) diiodide ( 2), respectively. Reaction of {2,6-[bis(dimethylamino)methyl]phenyl}(4-tolyl)tin(II) with diiodine gives {2,6-[bis(dimethylamino)Methyphenyl}(4-tolyl)tin(IV) diiodide ( 3) in quantitative yield. The crystal structures of 1 and 3 have been determined by X-ray diffraction methods. As a result of intramolecular coordination of the nitrogen atoms with the tin centers, the geometry about tin in both 1 and 3 is octahedral, while the carbon atoms bound to tin are in trans position. In 1 the two bromine atoms are cis to one another, as are the two nitrogen atoms, whereas in 3 the two iodine atoms, like the two nitrogen atoms, are trans to one another. 1H, 13C and 119Sn solution NMR spectroscopic studies of 1–3 show that they retain the structures found in the solid state.