alpha-P4S3I2, alpha-P4Se3I2, and P3Se4I were reacted with primary and secondary amines in CS2. The reaction yields exo-exo isomeres of alpha-P3S3L2 and alpha-P4Se3L2, the N-bridged compounds alpha-P4S3L' and P3Se4L, with L = NHR1, NPhR2 THC (R-1 = 'Bu, Ad, Ph, Flu, TPMP; R-2 = Me, Et, Pr-i), and L'=NR1. The P-31 NMR data of the compounds in CS2 solution were measured. By the reaction of alpha-P4Se3I2 With primary amines NH2'Bu and NH(2)Ad in CS2 an asymmetric isomer alpha-P(4)Se(3)Iendo(NHR1)exo was observed for the first time in the 31P NMR spectra. The influence of the ligands L on the P-31 NMR parameter of alpha-P4S3L2, alpha-P3Se3L2, and P3Se4L is discussed.