Ammonium Phenylphosphonamidodiselenoates and Phenylphosphonamidodi‐selenoic Diamides from the Selenation of Primary and Secondary Amines

By reacting two equivalents of primary or secondary amines with 2,4‐bis(phenyl)‐1,3‐diselenadiphosphetane‐2,4‐diselenide ( Woollins ' reagent) at room temperature a series of new ammonium phenylphosphonamidodiselenoates 1 – 7 have been obtained in good to excellent yields (70–99 %). The first metal complex of phenylphosphonamidodiselenoate, the complex of Cd 2 L 4 (L = [Se 2 PPh(NCH(CH 3 ) 2 ] – ) ( 8 ) has been prepared from the reaction of diisopropylamine N ‐isopropyl‐ P ‐phenylphosphonamidodiselenoate with Cd(CH 3 COO) 2 in dichloromethane. Upon heating to 130 °C the ammonium phenylphosphonamidodiselenoates lose hydrogen selenide leading to the corresponding phenylphosphonamidodiselenoic diamides 9 – 11 in almost quantitative yields. The same products 9 – 11 can also be prepared directly from the reaction of primary amines with Woollins ' reagent in refluxing toluene. Three representative X‐ray structures are described.