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

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 bix[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)methylphenyl}(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. H-1, C-13 and Sn-119 solution NMR spectroscopic studies of 1-3 show that they retain the structures found in the solid state.