A novel ate tin hydride complex, Li+ [n-Bu2SnI2H]-(I), was synthesized and characterized on the basis of its 119Sn NMR spectrum as a trigonal bipyramid (TBP) structure, in which two iodine atoms and one hydrogen atom occupy the apical and the equatorial positions, respectively. The apical iodine has much greater nucleophilicity than the hydrogen, so that the attack by iodide precedes the reduction by hydrogen, achieving regioselective 1, 4- ...