Abstract: | Reaction of a mixture of bicyclic phosphorus sulfide selenide iodides α‐P4SnSe3?nI2 (n = 0–3) with PriNH2 and Et3N gave corresponding diamides α‐P4SnSe3?n(NHPri)2 (n = 0–3) and imides α‐P4SnSe3?n(μ‐NPri) (n = 2–3), identified in solution by 31P NMR. In one isomer of α‐P4S2Se(μ‐NPri), the C2 symmetry of imides such as α‐P4S3(μ‐NPri) was broken, allowing relative assignment of 2J NMR couplings to the PNP bridge and the PSP bridge opposite to it. The coupling through the sulfur bridge was found to be reduced to ca. zero, in contrast to previous assumptions for this class of compounds. Ab initio models were calculated at the MPW1PW91/svp level for the sulfide selenide imides and for a selection of bond rotamers of the diamides, and at the MPW1PW91/LanL2DZ(d) level for the sulfide selenide diiodides. Different skeletal isomers were prevalent for the mixed chalcogenide diamides than for the diiodides, showing that exchange of chalcogen between skeletal positions took place in the amination reaction even at room temperature. Similar differences to those observed were predicted by the models, suggesting that equilibrium was attained. |